The colors of rocks Much of the color in the mineral world comes from

transition-metal ions. In fact, it is the Cr"+ within the crystal structure

of otherwise colorless aluminum oxide that makes rubies red. In
this chapter, we examine the transition metals and some of
their numerous applications as well as the structures and
properties of their compounds.

The Transition Elements and

Their Coordination Compounds
23.1 Properties of the Transition Elements
Electron Configurations
Atomic and Physical Properties
Chemical Properties
23.2 The Inner Transition Elements
The Lanthanides
The Actinides

23.3 Highlights of Selected Transition Metals

Chromium
Manganese
Silver
Mercury
23.4 Coordination Compounds
Structures of Complex Ions
Formulas and Names

Alfred Werner and Coordination Theory

Isomerism
23.5 Theoretical Basis for the Bonding
and Properties of Complexes
Valence Bond Theory
Crystal Reid Theory

ur exploration of the elements to this point is far from complete;

Oin fact, we have skirted the majority of them and some of the most
familiar. Whereas most important uses of the main-group elements involve
their compounds, the transition elements are remarkably useful in their
uncombined form. Figure 23.1 shows that the transition elements
(transition metals) make up the d block (B groups) and j' block (inner tran
sition elements).
In Chapter 22. you saw how two of the most important-copper and iron
are extracted from their ores. Aside from those two, with their countless essen
tial uses, many other transition elements are indispensable as well: chromium in
automobile parts, gold and silver in jewelry, tungsten in Iightbulb filaments, plat
inum in automobile catalytic converters, titanium in bicycle frames and aircraft
parts, and zinc in batteries, to mention just a few of the better known elements.
You may be less aware of zirconium in nuclear-reactor liners, vanadium in axles
and crankshafts, molybdenum in boiler plates, nickel in coins, tantalum in organ
replacement parts, palladium in telephone-relay contacts-the list goes on and on.
As ions. many of these elements also play vital roles in living organisms.
IN THIS CHAPTER .' We first discuss some atomic, physical, and chemical
properties of the transition elements and then focus on the chemistry of four
familiar ones: chromium, manganese. silver, and mercury. Next. we concentrate
on the most distinctive feature of transition element chemistry, the formation of
coordination compounds, substances that contain complex ions. We consider
two models that explain the striking colors of these compounds, as well as their
magnetic properties and structures, and then end with some essential bio
chemical functions of transition metal ions.

'1A
1

(1) 2A
(2)

3A 4A 5A 6A 7A
(13) (14) (15) (16) (17)

TRANSITIONELEMENTS

properties of light (Section 7.1)

electron shielding of nuclear charge
(Section8.2)
electron configuration, ionic size,and
magneticbehavior (Sections8.3to
8.5)
valencebond theory (Section
11.1)
constitutional, geometric,and optical
isomerism(Section15.2)
Lewisacidbaseconcepts(Section 18.9)
complex-ion formation
(Section19.4)
redox behavior and
standardelectrode potentials
(Section21.3)

78 ,.-66~
16128
38 148
(3)
(4) 58
(5) '68
(6) (7) (8) (9) (10) (11) 1(12)

14
5

La

r-

6
Hf

Ta

21
Sc

22
Tl

23
V

24
Cr

25
Mn

28
Fe

27
Co

28

NI

29
Cu

30
Zn

39
V

40
Zr

41 42
Nb Mo

43
Tc

44
Ru

45
Rh

46
Pd

47
Ag

48
Cd

57 72 73 74 75 76 77
pt
Re Os Ir
Au Hg

78

79

eo

89

104 105 106 107 108 109 110 111 112

Db Sg Bh Hs Mt Ds

.A_c -'- Rf

:' INNERTRANSITIONELEMENTS
(block

58

59
Pr

61 62 63
Nd Pm Sm Eu

90

91
Pa

92
U

Ce
Th

Figure 211 The transition

93
Np

--65

Tb

BB
Dy

67
Ho

66
Er

94 95 96 97
Pu Am Cm Bk

98
Cf

99
Es

100 101 102 103

Fm Md No Lr

60

elements

84
Gd

Id block)

69 70
Tm Vb

and inner transition elements

71
Lu

If block)

in the

periodic table.

1003

Chapter

100

Scandium, Sc; 38(3)

Titanium, Ti; 4B(4)

23 The Transition Elements and Their Coordination Compounds

Vanadium, V; 5B(5)

Chromium, Cr; 68(6)

Manganese, Mn; 78(7)

Figure III The Period 4 transition metals.

Samples of all ten elements appear as
pure metals, in chunk or powder form,
in periodic-table order on this and the
facing page.

23.1 PROPERTIES OF THE TRANSITION ELEMENTS

The transition elements differ considerably in physical and chemical behavior
from the main-group elements. In some ways. they are more uniform: main-group
elements in each period change from metal to nonmetal, but all transition ele
ments are metals. In other ways, the transition elements are more diverse: most
main-group ionic compounds are colorless and diamagnetic, but many transition
metal compounds are highly colored and paramagnetic. We first discuss electron
configurations of the atoms and ions, and then examine certain key properties of
transition elements, with an occasional comparison to the main-group elements.

Electron Configurations of the Transition Metals and Their Ions

As with any of the elements. the properties of the transition elements and their com
pounds arise largely from the electron configurations of their atoms (Section 8.3)
and ions (Section 8.5). The d-block (B-group) elements occur in four series that
lie within Periods 4 through 7 between the last ns-block element [Group 2A(2)]
and the first np-block element [Group 3A(13)]. Each series represents the filling
of five d orbitals and, thus, contains ten elements. In 1996 and 1997, elements
110 through 112 were synthesized in particle accelerators, so the Period 7 series
is complete; rhus, all 40 d-block transition elements are known. Lying between
the first and second members of the d-block transition series in Periods 6 and 7
are the inner transition elements, whose f orbitals are being filled.
Even though there are several exceptions, in general, the condensed ground
state electron configuration for the elements in each d-block series is
[noble gas] ni(n - l)d .... with n = 4 10 7 and x = 1 10 10
In Periods 6 and 7, the condensed configuration includes the f sublevel:
[noble gas] ni(n - 2)/4(n - l)d", with n = 6 or 7
The partial (valence-level) electron configuration for the d-block elements
excludes the noble gas COreand the filled inner f sublevel:
ns2(n - 1)d"T
The first transition series occurs in Period 4 and consists of scandium (Sc)
through zinc (Zn) (Figure 23.2 and Table 23.1). Scandium has the electron con
figuration [Ar] 4i3d', and the addition of one electron at a time (along with one
proton in the nucleus) first half-fills, then fills, the 3d orbitals across the periodic
table to zinc. Recall that chromium and copper are two exceptions to this general
pattern: the 4s and 3d orbitals in Cr are both half-filled to give [Ar] 4S13d5, and
the 4s in Cu is half-filled to give [Ar] 4s13dlO. The reasons for these exceptions
involve the change in relative energies of the 4s and 3d orbitals as electrons are
added across the series and the unusual stability of half-filled and filled sublevels.
Transition metal ions form through the loss of the I7S electrons before the
(11 - Ltd electrons. Therefore, the electron configuration of Ti2+ is [Ar] 3d2, not
[Ar] 4s2, and T?+ is referred to as a d2 ion. Ions of different metals with the
same confiruration often have similar properties. For example, both Mn2+ and
Fe3+ are d ions; both have pale colors in aqueous solution and. as we'll discuss
later, form complex ions with similar magnetic properties.
Table 23.1 shows a general pattern in number of unpaired electrons (or half
filled orbitals) across the Period 4 transition series. Note that the number increases

23.1

Iron, Fe; 88(8)

Cobalt, Co; 88(9)

1~~tI!!O1r1bital
Element

Properties of the Transition Elements

Nickel,Ni; 88(10)

Occueancl ofthe Period 4 Transition Metals

Partial Orbital Diagram

4s

3d

Sc

IT!]

Ti

[TI]

IT!]

t tl
t t t

Cr

ITJ

[TI]
[TI]

Mn
Fe

Copper, Cu; 18(11)

It

Unpaired Electrons
4p

I
2
3

t t t

tl

t r 1'1
IH 11' l' t 1'1
t t

6
5
4

Co

IT!] IHIt! 1'1 t tl

Ni

[TI]

ITJ

Cu

[TI]

Zn

IH It! It!
11'
IHlnl1'!lnlHI
IHIHIHI1'!I1'J,1

1'1

in the first half of the series and, when pairing begins, decreases through the sec
ond half. As you'll see, it is the electron configuration of the transition metal atom
that correlates with physical properties of the element, such as density and mag
netic behavior, whereas it is the electron configuration of the ion that determines
the properties of the compounds,

SAMPLE

PROBLEM

21.1

Writing Electron Configurations of Transition

Metal Atoms and Ions

Problem Write condensed electron configurations for the following: (a) Zr; (b) y3";
(c) M03+, (Assume that elements in higher periods behave like those in Period 4,)
Plan We locate the element in the periodic table and count its position in the respective
transition series, These elements are in Periods 4 and 5, so the general configuration is
[noble gas] /ls2(n - I)d". For the ions, we recall that ns electrons are lost first.
Solution (a) Zr is the second element in the 4d series: [Kr] 5s~4d2.
(b) Y is the third element in the 3d series: [Ar] 4i3d~, In forming v". three electrons
are lost (two 4s and one 3d), so y3+ is a d2 ion: [Ar] 3d2
(c) Mo lies below Cr in Group 6B(6). so we expect the same exception as for Cr. Thus,
Mo is [Kr] 5s14d5, To form the ion, Mo loses the one 5s and two of the 4d electrons, so
M03+ is a d3 ion: [Kr] 4dJ,
Check Figure 8.11 (p, 302) shows we're correct for the atoms. Be sure that charge plus
number of d electrons in the ion equals the sum of outer sand d electrons in the atom,

FO LLOW-UP
(a) Ag ":
Ir3~.

PROBLEM 21.1

(b) Cd2+; (c)

Write partial electron configurations for the following:

1005

Zinc, Zn; 28(12)

100

Chapter

23
Transition
and Their
Coordination Compounds
23.1The
Properties
of Elements
the Transition
Elements

100

Atomic and Physical Properties of the Transition Elements

The atomic properties of the transition elements contrast in several ways with
those of a comparable set of main-group elements.

Trends Across a Period Consider the variations in atomic size. electronegativity,

and ionization energy across Period 4 (Figure 23.3):

A Atomic radius(pm)

B Electronegativity

C First ionizationenergy (kJ/mol)

Ul#iili1I

Horizontaltrends in key
atomic properties of the Period 4
elements. The atomic radius (A). electro
negativity (B). and first ionization energy
(C) of the elements in Period 4 are Shown
as posts of different heights, with darker
shades for the transition series. The tran
sition elements exhibit smaller. less
regular changes for these properties than
do the main-group elements.

Atomic si:e. Atomic size decreases overall across the period

(Figure 23.3A). However. there is a smooth, steady de
crease across the main groups because the electrons are
added to outer orbitals, which shield the increasing nuclear
charge poorly. This steady decrease is suspended throughout the transition
series, where atomic size decreases at first but then remains fairly constant.
Recall that the d electrons fill inlier orbitals, so they shield outer electrons from
the increasing nuclear charge very efficiently. As a result. the outer 4s elec
trons are not pulled closer.
Electronegativity. Electronegativity generally increases
across the period but. once again, the transition elements
exhibit a relatively small change in electronegativity (Figure
23.3B), consistent with the relatively small change in size.
In contrast, the main groups show a steady, much steeper increase between the
metal potassium (0.8) and the nonmetal bromine (2.8). The transition elements
all have intermediate electronegativity values, much like the large, metallic
members of Groups 3A(13) to 5A(15).
Ionization energy. The ionization energies of the Period 4
main-group elements rise steeply from left to right, more
than tripling from potassium (419 kl/mol) to krypton
(1351 kJ/mol), as electrons become more difficult to remove
from the poorly shielded, increasing nuclear charge. In the transition metals,
however, the first ionization energies increase relatively little because the inner
3d electrons shield effectively (Figure 23.3C); thus, the outer 4s electron expe
riences only a slightly higher effective nuclear charge. [Recall from Section 8.4
that the drop at Group 3A( 13) occurs because it is relatively easy to remove
the first electron from the outer np orbital.]

Trends Within a Group Vertical trends for transition elements are also different
from those for the main groups.

Atomic size. As expected, atomic size increases from Period 4 to 5, as it does

for the main-group elements. but there is virtually no size increase from
Period
5 to 6 (Figure 23.4A). Remember that the lanthanides, with their buried 4f sub
level, appear between the 4d (Period 5) and 5d (Period 6) series. Therefore, an
element in Period 6 is separated from the one above it in Period 5 by 32 ele
ments (ten 4d, six 5p, two 6s, and fourteen 4f orbitals) instead of just 18. The
extra shrinkage that results from the increase in nuclear charge due to the addi
tion of 14 protons is called the lanthanide contraction. By coincidence. this
decrease is about equal to the normal increase between periods, so the Peri
ods 5 and 6 transition elements have about the same atomic sizes.
Electronegativity. The vertical trend in electronegativity seen in most transition
groups is opposite the trend in main groups. Here, we see an increase in elec
tronegativity from Period 4 to Period 5. but then no further increase in Period
6 (Figure 23.4B). The heavier elements, especially gold (EN = 2.4), become
quite electronegative, with values exceeding those of most metalloids and even
some nonmetals (e.g., EN of Te and of P = 2.1). (In fact, gold forms the salt
like CsAu and the Au- ion, which exists in liquid ammonia.) Although the

200

----

L.l'

y\

175

2.2

~
>
~en

, HI

f))

:::I

' C

150

s~Zr

(I)

1"

....,

_1200
(5

~1000
e-,

Ts

iii
u::

~12.0

Hf~-M~

600

24,0
a
I

800

~ 21.0

115.0

(I)

'c
.2

1.6

1,0

100
A

c;
OJ

2.0
1.8

ts
(I)
W 1.4
1.2

Mo

v --- ......
Cr

B 125
<t

Au

2.4

3d series, Period4
4d series, Period5
5d series, Period6

Cr

5B
(5)

6B
(6)

?:'iii 9.0
c
OJ
0 6.0

T<

t.:

400

3.0
3B
(3)

Ul:1'J:Jitl

4B
(4)

7B
(7)

8B
(8)

8B
(9)

8B
(10)

lB
(11)

2B
(12)

Group numbers

Vertical trends in key properties within the transition

elements. The trends are unlike those for the main-group elements in

38
(3)

4B
(4)

58
(5)

68
(6)

78
(7)

8B
(8)

8B
(9)

88
(10)

18
(11)

28
(12)

Groupnumbers

transition group. C, First ionization energies are highest at the bottom

of a transition group. D, Densities increase down a transition group
be cause mass increases faster than volume.

several ways: A, The second and third members of a transition metal

group are nearly the same size. B, Electronegativity Increases down a

atomic size increases slightly from the top to the bottom of a group, the nuclear
charge increases much more. Therefore, the heavier transition metals exhibit
more covalent character in their bonds and attract electrons more strongly than
do main-group metals.
Ionization energy. The relatively small increase in size combined with the rel
atively large increase in nuclear charge also explains why the first ionization
energy generally increases down a transition group (figure 23.4C). This trend
also runs counter to the pattern in the main groups, in which heavier members
are so much larger that their outer electron is easier to remove.
Density. Atomic size. and therefore volume, is inversely related to density.
Across a period, densities increase. then level off, and finally dip a bit at the
end of a series (Figure 23.40). Down a transition group, densities increase
dramatically because atomic volumes change little from Period 5 to 6, but
atomic masses increase significantly. As a result, the Period 6 series contains
some of the densest elements known: tungsten, rhenium, osmium, iridium, plat
inum, and gold have densities about 20 times that of water and twice that of
lead.

Chemical Properties of the Transition Metals

Like their atomic and physical properties, the chemical properties of the transi
tion elements are very different from those of the main-group elements. Let's
examine the key properties in the Period 4 transition series and then see how
behavior changes within a group.

Oxidation States One of the most characteristic chemical properties of the tran

Figure 23.5 Aqueous oxoanions of transi

tion elements. A, Often. a given transition
element has multiple oxidation states.
Here, Mn is shown in the +2 (Mn2' , left),
the +6 (MnOl-, middle), and the + 7
states (MnO. ", right). B, The highest
pos sible oxidation state equals the group
number in these oxoanions: VO.3- (left),
Cr207'- (middle). and MnO. - (right).

sition metals is the occurrence of multiple oxidation states. For example, in their
compounds, vanadium exhibits two common positive oxidation states, chromium
three, and manganese three (Figure 23.5A), and many other oxidation states are
seen less often. Since the ns and (n - I)d electrons are so close in energy, tran
sition elements can use all or most of these electrons in bonding. This behavior
is markedly different from that of the main-group metals. which display one or.
at most, two oxidation states in their compounds.
The highest oxidation state of elements in Groups 38(3) through 78(7) is
equal to the group number, as shown in Table 23.2. These oxidation states are
seen when the elements combine with highly electronegative oxygen or fluorine.
For instance, in the oxoanion solutions shown in Figure 23.5B, vanadium occurs
as the vanadate ion (VO/-; O.N. of V = +5), chromium occurs as the dichro
mate ion (Cr20/-;
O.N. of Cr = +6), and manganese occurs as the perman
ganate ion (Mn04 -; O.N. of Mn = +7). Elements in Groups 8B(8), 8B(9), and
8B( 10) exhibit fewer oxidation states, and the highest state is less common and
never equal to the group number. For example, we never encounter iron in the
+8 state and only rarely in the +6 state. The +2 and +3 states are the most
common ones for iron" and cobalt, and the +2 state is most common for nickel,
copper. and zinc. The +2 oxidation state is common because 11-\;2 electrons are
readily lost.
Copper, silver, and gold (the coinage metals) in Group IB(ll) are unusual.
Although copper has a fairly common oxidation state of + I, which results from
loss of its single 4s electron, its most common state is +2. Silver behaves more
predictably, exhibiting primarily the + I oxidation state. Gold exhibits the +3
state and, less often, the + I state. Zinc, cadmium, and mercury in Group 2B(l2)
exhibit the +2 state, but mercury also exhibits the + I state in the Hg/+ ion,
with its Hg-Hg bond."
'Iron may seem to have unusual oxidation states in the common ores magnetite (FesO.) and
pyrite (FeS2),but this is not really the case. In magnetite, one-third of the metal ions are Fe2'
and two-thirds are Fe", which is equivalent to a 1:1 ratio of FeO:Fe203 and gives an overall
formula of Fe30. Pyrite contains Fe2+ combined with the disulfide ion, S.'-.
"some evidence suggests that the Hg/' ion may exist as an Hg atom bonded to an Hg" ion,
with the atom donating its two 6s electrons for the covalent bond.

Oxidation States and d-Orbital Occupancy of the Period 4

Transition Metals*

Oxidation
State
0

38
(3)

dS

dS

,p

68
(6)

Sc

58
(5)
V

dl

d2

d3

+1

+2
+3
+4
+5
+6
+7

88

Cr

78
(7)
Mn

48
(4)
Ti

d2
ell

dl

,{'

,p
d3

,p

,,'
til

(8)

Fe

ciS

d5

tf'
tf'

tr

ct

cf'

cl-I

d"

cP

,p

".1

cf'

dl

d2

ell

dl

ct'

"The most important orbital occupancies are in color.

,p

88
(9)
Co

(10)
Ni

18
(11)
Cu

28
(12)
Zn

dS

dlo

dl!l

d7

dS

dlo

tP

<Ix

cf!

d'

,p

d~

d5

,{>

cf'

88

dIll

Metallic Behavior and Reducing Strength Atomic size and oxidation state have a
major effect on the nature of bonding in transition metal compounds. Like the
metals in Groups 3A(l3), 4A(14), and SA(lS), the transition elements in their

ItW),!,

Standard Electrode
Potentials of Period 4 M2+ Ions

that allows rapid reaction only with hot water or steam.

Color and Magnetism of Compounds

MOST main-group ionic compounds are color

less because the metal ion has a filled outer level (noble gas electron configura
tion). With only much higher energy orbitals available to receive an excited
electron, the ion does not absorb visible light. In contrast, electrons in a partially
filled d sublevel can absorb visible wavelengths and move to slightly higher
energy d orbitals. As a result. many transition metal compounds have striking col
ors. Exceptions are the compounds of scandium, titanium(IV), and zinc, which
are colorless because their metal ions have either an empty d sublevel (ScH or
Ti4+: [Ar] 3do) or a filled one (Zn2+: [Ar] 3d'o) (Figure 23.6).
Magnetic properties are also related to sublevel occupancy (Section 8.5).
Recall that a paramagnetic substance has atoms or ions with unpaired electrons,
which cause it to be attracted to an external magnetic field. A diamagnetic sub
stance has only paired electrons, so it is unaffected (or slightly repelled) by a
magnetic field. Most main-group metal ions are diamagnetic for the same reason
they are colorless: all their electrons are paired. In contrast, many transition metal
compounds are paramagnetic because of their unpaired d electrons. For exam
ple, MnS04 is paramagnetic, but CaS04 is diamagnetic. The Ca2+ ion has the
electron configuration of argon, whereas Mn2+ has a d5 configuration. Transition
metal ions with a dO or d'0 conliguration are also colorless and diamagnetic.

Figure23.6Colors of representative compounds of the Period 4

tran sition metals. Staggered from left to right, the compounds are

drate (light pink), potassium ferrlcyanide (red-orange), cobatt(lI) chlo

ride
hexahydrate
(violet),
nickel(lI)
nitrate
hexahydrate
(green),copper(lI) sulfate Half-Reaction
pentahydrate (blue), and zinc F>
sulfate
(V)
That
is, ionic(white).
bond
heptahydrate

scan dium oxide (white), titanium(lV) oxide (white), vanadyl sulfate

lower oxidation
states
behave
chemically
more
like metals.
dihydrate
(light blue),
sodium
chromate
(yellow),
manganese(lI)
chloride
tetrahying is more
prevalent for the lower oxidation states, and covalent

bonding is more
prevalent for (he higher states. For example, at room temperature, TiCl2 is an
ionic solid, whereas TrCl, is a molecular liquid. In the higher oxidation states, the
atoms have higher charge densities, so they polarize the electron clouds of the
nonmetal ions more strongly and the bonding becomes more covalent. For the
same reason, the oxides become less basic as the oxidation state increases: TiO
is weakly basic in water. whereas TiOz is amphoteric (reacts with both acid and
base).
Table 23.3 shows the standard electrode potentials of the Period 4 transition
metals in their +2 oxidation state in acid solution. Note that, in general, reduc
ing strength decreases across the series. All the Period 4 transition metals, except
copper, are active enough to reduce H+ from aqueous acid to form hydrogen gas.
In contrast to the rapid reaction at room temperature of the Group IA(l) and
2A(2) metals with water, however, the transition metals have an oxide coating

TI2+(aq) + 2ey2+(aq) + 2ec2+(aq) + 2eMn2+(aq) + 2eFe2+(aq) + Ze "

Co2+(aq) + 2eNi2+(aq) + 2eCuz+(aq)
Zn2+(aq)

::;::=: Ti(s)

-1.63

~
~
~
~

Crts)
Mn(s)
Fe(s)

Cots)

+ 2e- ~
+ 2e- ~

Cu(s)

-1.19
-0.91
-1.l8
-0.44
-0.28
-0.25
0.34
-0.76

Yes)

::;::=: Ni(s)
Zn(s)

Chapter 23 The23.2
TransitionElementsandTheir
The Inner Transition Elements
CoordinationCompounds

101

10

Chemical Behavior Within a Group The increase in reactivity going down a group
of main-group metals, as shown by the decrease in first ionization energy (IE.),
does not occur going down a group of transition metals. Consider the chromium
(Cr) group [6B(6)J, which shows a typical pattern (Table 23.4). lEI increases
down the group, which makes the two heavier metals less reactive than the light
est one. Chromium is also a much stronger reducing agent than molybdenum (Mo)
or tungsten (W), as shown by the standard electrode potentials.

'mMII"

Some Properties of Group 6B(6) Elements

Element
Cr
Mo

F> (V)for

Atomic
Radius (pm)

IE, (kJ/mol)

MH(aq)IM(s)

128
139
139

653
685
770

-0.74
-0.20
-0.11

The similarity in atomic size of Period 5 and 6 members also leads to simi
lar chemical behavior, a fact that has some important practical consequences.
Because Mo and W compounds behave similarly, for example, their ores often
occur together in nature, which makes the elements very difficult to separate from
each other. The same situation occurs with zirconium and hafnium in Group 4B(4)
and with niobium and tantalum in Group 5B(5).

All transition elements are metals. Atoms of the d-block elements have (n - 1)d
orbitals being filled, and their ions have an empty ns orbital. Unlike the trends in the
main-group elements, atomic size, electronegativity, and first ionization energy
change
relatively little across a transition series. Because of the lanthanide contraction,
atomic
Size changes little from Period 5 to 6 in a transition metal group; thus,
electronega tivity, first ionization energy. and density increase down a group.
Transition metals typ ically have several oxidation states. with the +2 state most
common. The elements
exhibit more metallic behavior in their lower states. Most Period 4 transition metals
are active enough to reduce hydrogen ion from acid solution. Many transition metal
com pounds are colored and paramagnetic because the metal ion has unpaired d
electrons.

A Remarkable Laboratory Feat

The discovery of the lanthanides is a
testi mony to the remarkable laboratory
skills of 19th-century chemists. The two
mineral sources, ceria and yttria, are
mixtures of compounds of all 14
lanthanides: yttria also includes oxides
of Sc, Y, and La. Pu rification of these
elements was so diffi cult that many
claims of new elements turned out to be
mixtures of similar ele ments. To
confuse matters, the periodic table of
the time had space for only one element
between Sa and Hf, which turned out to
be La. Not until 19.13,when the
atomic-number basis of the table was es
tablished. did chemists realize that 14
new elements could fit, and in 1918,
Niels Bohr proposed that the II = 4 level
be ex
panded to inelude thef sublevel.

23.2

THE INNER TRANSITION ELEMENTS

The 14 lanthanides-cerium
(Ce: Z '" 58) through lutetium (Lu; Z = 71)-lie
between lanthanum (Z = 57) and hafnium (Z = 72) in the third d-block transi
tion series. Below them are the 14 radioactive actinides, thorium (Th; Z = 90)
through lawrencium (Lr; Z = 103), which lie between actinium (Ac; Z = 89) and
rutherfordium (Rf: Z '" 104). The lanthanides and actinides are called inner tran
sition elements because. in most cases, their seven inner 4f or Vorbitals are being
filled.

The Lanthanides
The lanthanides are sometimes called the rare earth elements, a term referring to
their presence in unfamiliar oxides. but they are actually not rare at all. Cerium
(Ce), for instance, ranks 26'h in natural abundance (by mass %) and is five times
more abundant than lead. All the lanthanides are silvery, high-melting (800C to
1600C) metals. Their chemical properties represent an extreme case of the small
variations typical of transition elements in a period or a grouP. which makes the
lanthanides very difficult [0 separate.

The natural co-occurrence of the lanthanides arises because they exist as MH

ions of very similar radii in their common ores. Most lanthanides have the ground
state electron configuration [Xe] 6sL4Jx5do, where x varies across the series. The
three exceptions (Ce, Gd, and Lu) have a single electron in one of their 5c1
orbitals: Ce ([Xe] 6s24t5dl) forms a stable 4+ ion with an empty (/0) sublevel,
and the Gd3+ and Lu3+ ions have a stable half-filled V7) or filled V14) sublevel.
Lanthanide compounds and their mixtures have many uses. Several oxides
are used for tinting sunglasses and welder's goggles and for adding color to the
fluorescent powder coatings in TV screens. High-quality camera lenses incorpo
rate La203 because of its extremely high index of refraction. Samarium forms an
alloy with cobalt, SmCos, that is used in the strongest known permanent magnet
(see Sample Problem 23.2). Two industrial uses account for more than 60% of
rare earth applications. In gasoline refining, the zeolite catalysts (Gallery, p. 581)
used to "crack" hydrocarbon components into smaller molecules contain 5% by
mass rare earth oxides. In steelmaking. a mixture of lanthanides. called misch
metal. is used to remove carbon impurities from molten iron and steel.

SAMPLE PROBLEM

13.1

Finding the Number of Unpaired Electrons

Problem The alloy SmCo, forms a permanentmagnet becauseboth samariumand

cobalt have unpairedelectrons.How many unpairedelectronsare in the Sm atom (Z =

62)? Plan We write the condensedelectron configurationof Sm and then, using Hund's
rule and the aufbau principle. place the electrons in a partial orbital diagram and
count the unpairedelectrons.
Solution Samariumis the eighth elementafter Xe. Two electronsgo into the 6s
sublevel. In general. the 4f sublevel fills before the 5d (among the lanthanides,only
Ce, Gd, and Lu have Sd electrons),so the remainingelectronsgo into the 41. Thus. Sm is
[Xe] 6s24f6. There are seven.f orbitals.so each of the six.f electrons enters a
separateorbital:

[TI] Irl1'I1'I1'I1'I1'1

4f

6s

Sd

6p

Thus. Sm has six unpairedelectrons.

Check Six 4f e- plus two 6s e- plus the 54 e- in Xe gives 62. the atomicnumber of
Sm.

FOLLOW-UP

PROBLEM

21.2 How many unpairedelectrons are in the Er3+

ion?

The Actinides
All actinides are radioactive. Like the lanthanides, they share very similar phys
ical and chemical properties. Thorium and uranium occur in nature, but the
transuranium elements, those with Z greater than 92, have been synthesized in
high-energy particle accelerators, some in only tiny amounts (Section 24.3). In
fact, macroscopic samples of mendelevium (Md), nobelium (No), and lawrencium
(Lr) have never been seen. The actinides that have been isolated are silvery and
chemically reactive and. like the lanthanides. form highly colored compounds.
The actinides and lanthanides have similar outer-electron configurations. Although
the + 3 oxidation state is characteristic of the actinides, as it is for the lanthanides,
other states also occur. For example, uranium exhibits +3 through +6 states. with
the +6 state the most prevalent; thus, the most common oxide of uranium is U03 .

. SECTION SUMMA
There are two series of inner transition elements.The lanthanides (4f series) have a
common +3 oxidation state and exhibit very Similar properties. The actinides
(5f series) are radioactive. All actinides have a +3 oxidation state; several, including
uranium,have higher states as well.

23.3

HIGHLIGHTS OF SELECTEDTRANSITION METALS

Let's investigate several transition elements, focusing on the general patterns in

the aqueous chemistry of each. We examine chromium and manganese from
Period 4, silver from Period 5, and mercury from Period 6.

Chromium
Chromium is a very shiny, silvery metal, whose name (from the Greek chroma,
"color") refers to its many colorful compounds. A solution of C~+ is deep violet,
for example, and a trace of C~+ in the AI20} crystal structure gives ruby its beau
tiful red hue (see photo p. 1002). Chromium readily forms a thin, adherent, trans
parent coating of Cr203 in air, making the metal extremely useful as an attractive
protective coating on easily corroded metals, such as iron. "Stainless" steels often
contain as much as 18% chromium by mass and are highly resistant to corrosion.
With six valence electrons ([Ar] 4s13d5). chromium occurs in all possible pos
itive oxidation states, but the three most important are +2, + 3, and +6 (see Table
23.2). In its three common oxides, chromium exhibits the pattern seen in many
elements: nonmetallic character and oxide acidity increase with metal oxidation
state. Chromium(Il) oxide (CrO) is basic and largely ionic. lt forms an insoluble
hydroxide in neutral or basic solution but dissolves in acidic solution to yield the
Cr2+ ion:
CID(s) + 2H+(aq) -

Cr2~(aq) + H20(I)

Chromium(Ill) oxide (Cr203) is amphoteric, dissolving in acid to yield the violet

Cr3+ ion,

r
r

CrO/-

"'-1260/

Cr203(S)

6H+(aq) -

2Cr3+(aq)

3H20(l)

and in base to form the green Cr(OH)4- ion:

Cr203(S)+ 3H20U)

20H-(aq) -

2Cr(OH)4-(aq)

Thus, chromium in its +3 state is similar to the main-group metal aluminum in

several respects, including its amphoterism (Section 19.4).
Deep-red chromium(VI) oxide (Cr03) is covalent and acidic, forming chromic
acid (H2Cr04) in water,
+ H20(l) H2Cr04(aq)
Cr03(S)

which yields the yellow chromate ion (Cr042-) in base:

H2Cr04(aq)

cr2ol-

20H-(aq) -

CrO/-(aq)

2H20(1)

In acidic solution, the chromate ion immediately forms the orange dichromate ion
(Cr2072-):
Because both ions contain chromium(VI), this is not a redox reaction; rather, it
is a dehydration-condensation, as you can see from the structures in Figure 23.7.
Hydrogen-ion concentration controls the equilibrium position: yellow Cr042- pre
dominates at high pH and orange Cr20/at low pH. The bright colors of
chromium(VI) compounds lead to their wide use in pigments for artist's paints
and ceramic glazes. Lead chromate (chrome yellow) is used as an oil-paint color,
and also in the yellow stripes that delineate traffic lanes.
Chromium metal and the Cr2+ ion are potent reducing agents. The metal dis
places hydrogen from dilute acids to form blue Cr2+(aq), which reduces O2 in
air within minutes to form the violet Cr3+ ion:

Figure 23.7 The bright colors of

chromium(Vl) compounds. A, Structures
of the chromate (crO.2-) and dichromate
(Cr20l-) ions. e, Samples of K2CrO.
(yellow) and K2Cr207(orange).

4Cr2+(aq)

+ 02(g) + 41-l+(aq)

,. 4Cr1+(aq)

21-120(/)

~vcrall

1.64 V

Chromium(VI) compounds in acid solution are strong oxidizing agents (concen

trated solutions are extremely corrosive!), the chromium(VI) being readily reduced
to chromiumtlll):
J!1

= 1.33 V

10

Chapter21.1
23 Highlights
The Transition
Elements
and Their
Coordination Compounds
of Selected
Transition
Metals

lOB

This reaction is often used to determine the iron content of a water or soil sam
ple by oxidizing Fe2+ (0 Fe3+ ion. In basic solution, the crO/- ion, which is a
much weaker oxidizing agent, predominates:
CrOl- (aq) + 4H20(l) + 3e- --+ Cr(OHh(s) + 50H - (aq)
Efl = -0.13 V

The Concept of Valence-State Electronegativity Why does oxide acidity increase

with oxidation state? And how can a metal, like chromium, form an oxoanion?
To answer such questions, we must apply the concept of electronegativity to the
various oxidation states of an element. A metal in a higher oxidation state is more
positively charged, which increases its attraction for electrons; in effect, its elec
tronegativity increases. This effective electronegativity, called valence-state elec
tronegativity, also has numerical values. The electronegativity of chromium metal
is 1.6, close to that of aluminum (1.5), another active metal. For chromium(III),
the value increases to 1.7, still characteristic of a metal. However, the elec
tronegativity of chromiurnt Vl) is 2.3, close to the values of some nonmetals,
such as phosphorus (2.1), selenium (2.4), and carbon (2.5). Thus, like P in
P043-, Cr in chromium(VI) compounds often occurs covalently bonded at the
center of the oxoanion of a relatively strong acid.

Manganese
Elemental manganese is hard and shiny and. like vanadium and chromium, is used
mostly to make steel alloys. A small amount of Mn 1%) makes steel easier to
roll, forge, and weld. Steel made with 12% Mn is tough enough to be used for
naval armor, front-end loader buckets (see photo), and other extremely hard steel
objects. Small amounts of manganese are added to aluminum beverage cans and
bronze alloys to make them stiffer and tougher as well.
The chemistry of manganese resembles that of chromium in some respects.
The free metal is quite reactive and readily reduces H+ from acids, forming the
pale-pink Mn2+ ion:
Mn(s) + 2H+(aq) Mn2+(aq) + H2V;)
Efl = 1.18 Y
Like chromium, manganese can use all its valence electrons in its compounds,
exhibiting every possible positive oxidation state, with the +2, +4, and + 7 states
most common (Table 23.5). As the oxidation state of manganese rises, its valence
state electronegativity increases and its oxides change from basic to acidic. Man
ganese(ll) oxide (MnO) is basic, and manganese(lIl) oxide (Mn203) is
amphoteric. Manganese(IV) oxide (Mn02) is insoluble and shows no acid-base
properties. [It is used in dry cells and alkaline batteries as the oxidizing agent in
a redox reaction with zinc (Chapter 21. p. 932).J Manganese(YlI) oxide (Mn207)'

Oxidation state=
Example
Orbital occupancy
Oxide acidity

Mn(II)
Mn2+
d5
[BASIC

'Most common states in boldface.

Mnon)
Mn203
d4

Mn(IV)
Mn02
d3

Mn(YI)
MnO/dl

Mn(VII)
Mn04-

dO

Front-end loader parts are made of steel

containing manganese.

Sharing the Ocean's Wealth At their

current rate of usage, known reserves of
many key transition metals will be de
pleted in less than 50 years. Other
sources must be found. One promising
source is nodules strewn over large
portions of the ocean floor. Varying from
a few millime ters to a few meters in
diameter, these chunks consist mainly of
manganese and iron oxides, with oxides
of other elements present in smaller
amountS. Billions of tons exist, but
mining them presents ma jor technical
and
political
challenges.
Global
agreements have designated the ocean
floor as international property, so
cooperation will be required to mine the
nodules and share the mineral rewards.

which forms by reaction of Mn with pure O2, reacts with water to form perman
ganic acid (HMn04), which is as strong as perchloric acid (HCI04).
All manganese species with oxidation states greater than +2 act as oxidizing
agents. but the purple permanganate (Mn04 -) ion is particularly powerful. Like
ions with chromium in its highest oxidation state, Mn04 - is a much stronger oxi
dizing agent in acidic than in basic solution:
Mn04 -(aq) + 4H+(aq) + 3e- Mn02(S) + 2H20(I)
f!J = 1.68 V
Mn04 -(aq) + 2H20(l) + 3e- ----+ Mn02(S) + 40H-(aq)
l = 0.59 V
Unlike C?+ and Fe2+, the Mn2+ ion resists oxidation in air. The Cr2+ ion
is a d4 species and readily loses a 3d electron to form the d3 ion cil+, which is
more stable. The Fez+ ion is a d6 species, and removing a 3d electron yields the
stable, half-filled cl5 configuration of Fe3+. Removing an electron from Mnz+ dis
rupts its stable d5 configuration.

Silver
Silver, the second member of the coinage metals [Group l Btl l j], has been
admired for thousands of years and is still treasured for use in jewelry and fine
flatware. Because the pure metal is too soft for these purposes, however, it is
alloyed with copper to form the harder sterling silver. In former times, silver was
used in coins, but it has been replaced almost universally by copper-nickel alloys.
Silver has the highest electrical conductivity of any element but is not used in
wiring because copper is cheaper and more plentiful. In the past, silver was found
in nuggets and veins of rock, often mixed with gold, because both elements are
chemically inert enough to exist uncombined. Nearly all of those deposits have
been mined, so most silver is now obtained from the anode mud formed during
the electrorefining of copper (Section 22.4).
The only important oxidation state of silver is +1. Its most important solu
ble compound is silver nitrate, used for electroplating and in the manufacture of
the halides used for photographic film. Although silver forms no oxide in air, it
tarnishes to black AgzS by reaction with traces of sulfur-containing compounds.
Some polishes remove the Ag2S, along with some silver, by physically abrading
the surface. An alternative "home remedy" that removes the tarnish and restores
the metal involves hearing the object in a solution of table salt or baking soda
(NaHC03) in an aluminum pan. Aluminum, a strong reducing agent, reduces the
Ag + ions back to the metal:
2AI(s)

3Ag2S(s)

6H20(l) ---

2AI(OHh(s)

6Ag(s)

3H2S(g)

f!l

= 0.86 V

The Chemistry of Black-and-White Photography The most widespread use of sil

ver compounds-particularly the three halides AgCl, AgBr, and AgI-is in black
and-white photography, an art that applies transition metal chemistry and solution
kinetics. The photographic film itself is simply a flexible plastic support for the
light-sensitive emulsion, which consists of AgBr microcrystals dispersed in gela
tin. The five steps in obtaining a final photograph are exposing the film, devel
oping the image, fixing the image, washing the negative, and printing the image.
Figure 23.8 summarizes the first four of these steps. The process depends on sev
eral key chemical properties of silver and its compounds:
Silver halides undergo a redox reaction when exposed to visible light.
Silver chloride, bromide, and iodide are 110t water soluble.
Ag+ is easily reduced: Ag+(aq) + e " ----+ Ag(s); EO :0= 0.80
V.
Ag + forms several stable, water-soluble complex
ions.
1. Exposing the film. Light reflected from the objects in a scene-more light
from blight objects than from dark ones-enters the camera lens and strikes the
film. Exposed AgBr crystals absorb photons (hI!) in a very localized redox reac-

1015

23.3 Highlights of Selected Transition Metals

CD Expose.

Photons hit film: Br

is oxidized. Ag + is reduced.

Develop.

Additional Ag +

Is reduced.
----.--

Fix. Further

reduction of
Ag + is prevented by
forming Ag(S203 )l-(aq).

@ Wash.

Soluble species
are removed. leaving Ag
granules in place on film.

Ughttight
container
Hydroquinone
(H20)
Film

AgBr crystals
before developing

AgBr crystals
after developing

Negative

Figure 23.8 Steps in producing a black

andwhite negative.

tion. A Br" ion is excited by a photon and oxidized, and the released electron
almost immediately reduces a nearby Ag + ion:

.s: Br + e

BrAg+ + e- -Ag+ + Br" ~

Ag
Ag

Br

Wherever more light strikes a microcrystal. more Ag atoms form. The exposed
crystals are called a latent image because the few scattered atoms of photoreduced
Ag are not yet visible. Nevertheless, their presence as crystal defects within the
AgBr crystal makes it highly susceptible to further reduction.
2. Developing the image. The latent image is developed into the actual image
by reducing more of the silver ions in the crystal in a controlled manner. Devel
oping is a rate-dependent step: crystals with many photoreduced Ag atoms react
more quickly than those with only a few. The developer is a weak reducing agent
such as the organic substance hydroquinone (HZC6H402; H2Q) (see margin):
2Ag+(s)

H2Q(aq; reduced form) ---

2Ag(s)

+ Q(aq:

oxidized form)

+ 2H+Caq)

The reaction rate depends on H2Q concentration. solution temperature. and the
length of time the emulsion is bathed in the solution. After developing. approxi
mately 106 as many Ag atoms are present on the film as there were in the latent
image, and they form very small. black clusters of silver.
3. Fixing the image. After the image is developed. it must be "fixed"; that is,
the reduction of Ag + must be stopped, or the entire film will blacken on expo
sure to more light. Fixing involves removing the remaining Ag + chemically by
converting it to a soluble complex ion with sodium thiosulfate solution ("hypo"):
AgBr(s) + 2S20/-Caq) --- Ag(S203h3-(aq) + Br-(aq)
4. Washing the negative. The water-soluble ions are washed away in water.
Washing is the final step in producing a photographic negative. in which dark
objects in the scene appear bright in the image. and vice versa.

hydroquinone

quinone

1016

Chapter 23. The Transition Elements and Their Coordination Compounds

5. Printing the image. Through the use of an enlarger, the image on the neg
ative is projected onto print paper coated with emulsion (silver halide in gelatin)
and exposed to light, and the previous chemical steps are repeated to produce a
"positive" of the image. Bright areas on a negative, such as car tires, allow a great
deal of light to pass through and reduce many Ag+ ions on the print paper. Dark
areas on a negative, such as clouds. allow much less light to pass through and,
thus, much less Ag+ reduction. Print-paper emulsion usually contains silver chlo
ride, which reacts more slowly than silver bromide, giving finer control of the
print image. High-speed film incorporates silver iodide, the most light-sensitive
of the three halides.

Mercury
Mercury has been known since ancient times because cinnabar (HgS), its princi
pal ore, is a naturally occurring red pigment (vermilion) that readily undergoes a
redox reaction in the heat of a fire. Sulfide ion, the reducing agent for the process,
is already present as part of the ore:
HgS(s)

02(g) -

Hg(g)

S02(g)

The gaseous Hg condenses on cool nearby surfaces.

The Latin name hydrargyrum ("liquid silver") is a good description of mer
cury, the only metal that is liquid at room temperature. Two factors account for
this unusual property. First, because of a distorted crystal structure, each mercury
atom is surrounded by 6 rather than 12 nearest neighbors. Second, a filled, tightly
held d sublevel leaves only the two 6s electrons available for metallic bonding.
Thus, interactions among mercury atoms are relatively few and relatively weak
and, as a result, the solid form breaks down at - 38.9C.
Many of mercury's uses arise from its unusual physical properties. Its liquid
range (- 39C to 357C) encompasses most everyday temperatures, so Hg is com
monly used in thermometers. As you might expect from its position in Period 6
following the lanthanide contraction, mercury is quite dense (13.5 g/ml.), which
makes it convenient for use in barometers and manometers. Mercury's fluidity
and conductivity make it useful for "silent" switches in thermostats. At high pres
sures, mercury vapor can be excited electrically to emit the bright white light seen
in sports stadium and highway lights.
Mercury is a good solvent for other metals, and many amalgams (alloys of
mercury) exist. In mercury batteries, a zinc amalgam acts as the anode and
mercury(II) oxide acts as the cathode (Chapter 21, p. 933). In the mercury-cell
version of the chior-alkali process (Chapter 22, p. 995), mercury acts as the
cathode and as the solvent for the sodium metal that forms. Recall that, when
treated with water, the resulting sodium amalgam, Na(Hg), forms two important
by-products:
2Na(Hg) + 2H20(l) ~
2NaOH(aq}+ H2(g)
The mercury is released in this step and reused in the electrolytic cell. In view
of mercury's toxicity, which we discuss shortly, a newer method involving a
polymeric membrane is replacing the mercury-cell method. Nevertheless, past
contamination of wastewater from the chlor-alkali process and the disposal of old
mercury batteries remain serious environmental concerns.
The chemical properties of mercury are unique within Group 2B(l2). The
other members, zinc and cadmium, occur in the +2 oxidation state as dID ions,
but mercury occurs in the + 1 state as well, with the condensed electron
config uration [Xe] 6s'4/45dlD
We can picture the unpaired 6s electron
allowing two
Hg(I) species to form the diatomic ion [Hg-Hgf+
(written Hg22+), one of the

23.4

CoordinationCompounds

first species known with a covalent metal-metal bond (but also see the footnote
on p. 1008). Mercury's more common oxidation state is +2. Whereas HgF2 is
largely ionic, many other compounds, such as HgCl2, contain bonds that are pre
dominantly covalent. Most mercury(II) com~ounds are insoluble in water.
The common ions Zn2+, Cd2+, and Hg + are biopoisons. Zinc oxide is used
as an external antiseptic ointment. The Cd2+ and Hg2+ ions are two of the 80called toxic heavy-metal ions. The cadmium in solder may be more responsible
than the lead for solder's high toxicity. Mercury compounds have been used in
agriculture as fungicides and pesticides and in medicine as internal drugs, but
these uses have been largely phased out.
Because most mercury(ll) compounds are insoluble in water, they were once
thought to be harmless in the environment; but we now know otherwise. Micro
organisms in sludge and river sediment convert mercury atoms and ions to the
methyl mercury ion. CH3 - Hg + . and then to organomercury compounds. such as
dimethylmercury, CH3-Hg-CH3.
These toxic compounds are nonpolar and,
like chlorinated hydrocarbons, become increasingly concentrated in fatty tissues,
as they move up a food chain from microorganisms to worms to fish and, finally,
to birds and mammals. Indeed, fish living in a mercury-polluted lake or coastal
estuary can have a mercury concentration thousands of times higher than that of
the water itself.
The mechanism for the toxicity of mercury and other heavy-metal ions is not
fully understood. It is thought that the ions migrate from fatty tissue and bind
strongly to thiol (-SH) groups of amino acids in proteins, thereby disrupting the
proteins' structure and function. Because the brain has a high fat content, small
amounts of lead, cadmium, and mercury ions circulating in the blood become
deposited in the brain's fatty tissue, interact with its proteins, and often cause dev
astating neurological and psychological effects.

Chromium and manganese add corrosion resistance and hardness to steels. They
are typical of transition metals in having several oxidation states. Valence-state
elec tronegativity refers to the ability of an element in its various oxidation states to
attract bonding electrons. It increases with oxidation number. which is the reason
elements act more metallic (more ionic compounds, more basic oxides) in lower
states and more nonmetallic (more acidic oxides, oxoanions of acids) in higher
states. Cr and Mn produce H2 in acid. Cr(Vl) undergoes a pH-sensitive
dehydration-condensation reaction. Both Cr(Vl) and Mn(VlI) are stronger oxidizing
agents in acid than in base. The only important oxidation state for silver is +1. The
silver halides are light sensi tive and are used in photography. Mercury, the only
metal that is liquid at room tem perature, dissolves many other metals in important
applications. The mercury(l) ion is diatomic and has a metal-metal covalent bond.
The element and its compounds are toxic and become concentrated as they move
up a food chain.

23.4 COORDINATION COMPOUNDS

The most distinctive aspect of transition metal chemistry is the formation of coor
dination compounds (also called complexes). These are substances that contain
at least one complex ion, a species consisting of a central metal cation (either
a transition metal or a main-group metal) that is bonded to molecules and/or
anions called ligands. ln order to maintain charge neutrality in the coordina
tion compound, the complex ion is typically associated with other ions, called
counter ions.

1017

---_ .._.
N';~~~::-:7-:z:~:
~:-.~
Mad as a Hatter The felt top hat and
zany manner of the Mad Hatter in Alice
in Wonderland are literary references to
the toxicity of mercury compounds. Mer
cury(ll) nitrate and chloride were used
with HN03 to make felt for hats from an
imal hair. Inhalation of the dust
generated by the process led to "hatter's
shakes." abnormal behavior. and other
neurologi
cal
and
psychological
symptoms.

101
810

23.4 Coordination
Compounds
Chapter 23 The Transition
Elements and Their Coordination Compounds

101
In solid

3+

In solution

In solid
CI-

CI-

CINH3

H3~
H3N_

""co-----

3+

NH3

H3~
NH3 CI3

H3N~

H3N

l;o-----

/NH3

/~H3

NH3

NH3

[Co(NH3)61CI3(5)

CI-

NH3

CI-

H3N ----

""'-Pt"-_-"

NH3 Br2

NH3
CI-

(Co(NH3)613+(aq)

+ 3CI-(aq)

Figure 23.9 Components of a coordina

tion compound. Coordination com
pounds, shown here as models (top),
per spective drawings (middle), and
chemical formulas (bottom), typically
consist of a complex ion and counter
ions to neutral ize the charge. The
complex ion has a central metal ion
surrounded by ligands. A, When solid
[Co(NH3)6JCId3 issolves,
the complex ion and the counter ions
separate, but the ligands remain bound
to the metal ion. Six ligands around the
metal ion give the complex ion an octahe
dral geometry. B, Complex ions with a
central d" metal ion have four ligands
and a square planar geometry.

A typical coordination compound appears in Figure 23.9A: the coordination

compound is [Co(NH)6]CI3, the complex ion (always enclosed in square brack
ets) is [Co(NH)6]3+, the six NH3 molecules bonded to the central C03+ are li
gands, and the three CI- ions are counter ions. A coordination compound behaves
like all electrolyte in water: the complex ion and counter ions separate from each
other. But the complex ion behaves like a polyatomic ion: the ligands and cen
tral metal ion remain attached. Thus, as Figure 23.9A shows, 1 mol of
[Co(NH3)6]CI3 yields 1 mol of [Co(NH3)6]3+ions and 3 mol of Cl" ions.
We discussed the Lewis acid-base properties of hydrated metal ions, which
are a type of complex ion, in Section 18.9, and we examined complex-ion equi
libria in Section 19.4. In this section, we consider the bonding, structure, and
properties of complex ions.

Complex Ions: Coordination Numbers, Geometries, and Ligands

A complex ion is described by the metal ion and the number and types of ligands
attached to it. Its structure is related to three characteristics-coordination
num
ber, geometry, and number of donor atoms per ligand:
Coordination number. The coordination number is the number of ligand
atoms that are bonded directly to the central metal ion and is specific for a
given metal ion in a particular oxidation state and compound. The coordina
tion number of the C03+ ion in [Co(NH3)6)3+ is 6 because six ligand atoms
(N from NH3) are bonded to it. The coordination number of the Pt2+ ion in
many of its complexes is 4, whereas that of the Pt4+ ion in its complexes is
6. Copper(lI) may have a coordination number of 2, 4, or 6 in different com
plex ions. In general, the most common coordination number in complex iOI1S
is 6, but 2 and 4 are often seen, and some higher ones are also known.
Geometry. The geometry (shape) of a complex ion depends on the coordina
lion number and nature of the metal ion. Table 23.6 shows the geometries asso
ciated with the coordination numbers 2, 4, and 6. with some examples of each.
A complex ion whose metal ion has a coordination number of 2, such as
[Ag(NH3hJ+, is linear. The coordination number 4 gives rise to either of two
geometries-square planar or tetrahedral. Most dB metal ions form square pla
nar complex ions, depicted in Figure 23.9B. The dlo ions are among those that

_mIlt"

Coordination

Numbers and Shapes of Some Complex Ions

Coordination
Number

Shape

Linear

Squareplanar

Tetrahedral

[CU(CN)4]3-[,
Zn(NH3)4f+, [CdC14f-,
[MnC4]2-

Octahedral

[Ti(H20)613+,[V(CN)6]4-,
[Cr(NH3)4CI2j+
[FeCl(\]3-[Co(en)J]3+

Examples

[CuCI2r,[Ag(NH3h]+,
[AuCI:r
[Ni(CN)4f-, [PdCI4f-,
[Pt(NH3)4]2+[,Cu(NH3)4]2+

form tetrahedral complex ions. A coordination number of 6 results in an octa

hedral geometry, as shown by [Co(NH3)613+ in Figure 23.9A. Note the simi
larity with some of the molecular shapes in VSEPR theory (Section 10.2).
Donor atoms per ligand. The ligands of complex ions are molecules or anions
with one or more donor atoms that each donate a lone pair oj electrons to the
metal ion to form a covalent bond. Because they have at least one lone pair,
donor atoms often come from Group SA(l5), 6A(l6), or 7 A(17).
Ligands are classified in terms of the number of donor atoms, or "teeth," that
each uses to bond to the central metal ion. Monodentate (Latin, "one-toothed")
ligands. such as CI- and NH3, use a single donor atom. Bidentate ligands have
two donor atoms, each of which bonds to the metal ion. Polydentate ligands have
more than two donor atoms. Table 23.7 shows some common ligands in coordi
nation compounds; note that each ligand has one or more donor atoms (colored
type), each with a lone pair of electrons to donate. Bidentate and polydentate

'MMIIU

Some Common Ligands in Coordination

Ligand Type

Examples

Monodentate

HiS:

water

:NH3ammonia

Compounds

:F: -

fluorideion

:("1:-

chloride ion

I:C=N:]-

cyanideion

[:g-H]-

hydroxideion

[:"=c=r':]-

thiocyanateion

[:~-t'!=ol

nitrite ion

Lor_j

LorJ

.
[ ';0'].2. -

Bidentate

.p ~

H~C-C~2

H2!,!

C-C

:".b-:
"'0..:

!'!H2

ethylenediamine(en)

:6~t_CH,\2

oxalateion

:0:

Polydentate

"' / '
H

"

diethylenetriamine

:0:

..

..

:.0, :

CH2~~~6:.1. 4'

]5-

:0:

: O -P
-O -P -O . . P-II"O:.. .. " . .

H2C-CH2 CHz-CH2
[
H2/!,'!
~~H2
~ J

:N-CH2-CH2- N:

..

:0.. :
0.. :

triphosphateion

..
:

[ .. ..
:0

I /I

-C - CH2

:0:

'\

.. II -0.:.

CH2-C
:0:

ethyJenediaminetetraacetatioen (EDTA4-)

ligands give rise to rings in the complex ion. For instance, ethylenediamine
(abbreviated en in formulas) has a chain of four atoms (:N-C-C-N:),
so it
forms a five-membered ring, with the two electron-donating N atoms bonding to
the metal atom. Such ligands seem to grab the metal ion like claws, so a com
plex ion that contains them is also called a chelate (pronounced "KEY-late";
Greek chela, "crab's claw").

[Pb(EDTA))2-

Grabbing Ions Because it has 6 donor

atoms, [he erhylenediamineterraacerate
(EDTA4-)
ion forms very stable com
plexes with many metal ions. This prop
erty makes EDTA useful in treating
heavy-metal poisoning. Once ingested by
the patient, the ion acts as a scavenger to
remove lead and Other heavy-metal ions
from the blood and other body f uids.

Formulas and Names of Coordination Compounds

There are three important rules for writing the formulas of coordination com
pounds, the first two being the same for writing formulas of any ionic compound:
l. The cation is written before the
anion.
2. The charge of the cationis) is balanced by the charge of the anion(s).
3. In the complex ion, neutral ligands are written before anionic ligands, and the
formula for the whole ion is placed in brackets.
Let's apply these rules as we examine the combinations of ions in coordination
compounds. The whole complex ion may be a cation or an anion. A complex
cation has anionic counter ions, and a complex anion has cationic counter ions.
It's easy to find the charge of the central metal ion. For example, in
K2[Co(NH3)zCI4),two K+ counter ions balance the charge of the complex anion
[Co(NH3hCI4f-, which contains two NH3 molecules and four CI- ions as li
gands. The two NH~ are neutral, the four CI- have a total charge of 4-, and
the
entire complex ion has a charge of 2 -, so the central metal ion must be
C02+:
Charge of complex ion
2Charge of metal ion

Charge of metal ion

Charge of metal ion

+
+

total charge of ligands

1,(2X 0) + (4 X 1-)]

So,
= (2-) - (4-) = 2+
In the compound (Co(NH3)4CI21CIt,he complex ion is [Co(NH3)4CI2t and
one Cl " is the counter ion. The four NH3 ligands are neutral, the two CIligands have a total charge of 2 -, and the complex cation has a charge of I
+, so the central metal ion must be Co3+ [that is, 1+ = (3+) + (2-). Some
coordination compounds have a complex cation and a complex
anion, as in rCo(NH3)sBrh[Fe(CN)6]'
In this compound, the
complex cation is [Co(NH3hBrf+, with Co3+, and the complex anion is
[Fe(CN)6]4-, with Fe2+.
Coordination compounds were originally named after the person who first
prepared them or from their color, and some of these common names are still
used, but most coordination compounds are named systematically through a set
of rules:
1. The cation is named before the anion. In naming [Co(NH3)4CIz.lClf, or
exam
ple. we name the [Co(NH3)4CI2)+ion before the CI- ion. Thus, the name is
letraamminedichlorocobalt(flI) chloride

The only space in the name appears between the cation and the anion.
2. Within the complex iOI1, the ligands are named, in alphabetical order, before
the metal ion. Note that in the [Co(NH3)4CI2]+ ion of the compound
named in rule 1, the four NH3 and two CI- are named before the Co3+.
3. Neutral ligands generally have the molecule name, but there are a few excep
tions (Table 23.8). Anionic ligands drop the -ide and add -0 after the root
name .. thus, the name fluoride for the F- ion becomes the ligand name
fluoro. The two ligands in (Co(NH3)4C12+] are ammine (NH3) and chloro
(Cl") with ammine coming before chloro alphabetically.
4. A numerical prefix indicates the number of ligands of a. particular type. For
example. tetraammine denotes josr NH3 and dichloro denotes two C]-. Other
prefixes are tri-, penta-, and hexa-, These prefixes do not affect the alphabet
ical order; thus. tetraammine comes before dichloro. Because some ligand

23.4

Coordination

102

Compounds

Chapter 21 The Transition Elementsand Their Coordination Compounds

102

'mNIII:'

Names of Some Neutral and Anionic Ligands

Anionic

Neutral
Name

Formula

Name

Formula

Aqua
Ammine
Carbonyl
Nitrosyl

H 2O
NH3
CO
NO

Fluoro
0110ro
Bromo
Iodo
Hydroxo
Cyano

FCIBr-

1OHCN-

names already contain a numerical prefix (such as ethylenediamine),

we use bts
(2), tris (3), or tetrakis (4) to indicate the number of such ligands, followed by the
ligand

name in parentheses.

Therefore,

a complex

ion that has two

'MIlt. Names of Some

Metal Ions in Complex Anions

(Note that there is one K+ counter ion, so the complex anion has a charge of
1-. The five Cl- ligands have a total charge of S -, so Pt must be in the +4
oxidation state.) For some metals, we use the Latin rool with the -ate ending,
shown in Table 23.9. For example, the name for N!4[FeBr6] is
sodium hexabromoferrate(fI)

SAMPLE

PROBLEM

Coordination

23.3

Writing

Names and Formulas of

Compounds

Problem (a) What is the systematic name of Na3[AIF6]?

(b) What is the systematic name of [Co(enhCI2lN03?
(c) What is the formula of tetraamminebromochloroplatinum(IV) chloride?
(d) What is the formula of hexaamminecobalt(IJI) terrachloroferratetlll)?
Plan We use the rules that were presented above and refer to Tables 23.8 and 23.9.
Solution (a) The complex ion is [AlF6]3-. There are six (hexa-) F- ions (fiuoro) as li
gands, so we have hexafluoro. The complex ion is an anion, so the ending of the metal
ion (aluminum) must be changed to -ate: hexafluoroaluminate. Aluminum has only the + 3
oxidation state. so we do not use a Roman numeral. The positive counter ion is named
first and separated from the anion by a space: sodium hexafiuoroaluminate.
(b) Listed alphabetically, there are two CI- (dichloro) and two en [bis(ethyienediamine)]
as ligands. The complex ion is a cation, so the metal name is unchanged, but we specify
its oxidation state because cobalt can have several. One N03 - balances the I + cation
charge: with 2- for two CI- and 0 for two en, the metal must be cobalr(IlI). The word
nitrate follows a space: dichiorobis(ethylenediamine)cobalt(lll) nitrate.
(c) The central metal ion is written first. followed by the neutral ligands and then (in alpha
betical order) by the negative ligands. Tetraammine is four NH3, bromo is one Br -,
chloro is one Cl ", and platinatetlv') is Pt4+, so the complex ion is [Pt(NHJ)4BrClf+.
Its 2+ charge is the sum of 4+ for Pt4+, 0 for four NH3, 1- for one Br", and 1- for
one CI-. To balance the 2+
charge, we need two CIcounter
ions:
[Pt(t-.TH3)4BrCI]CI2'

ethylenediamine

ligands has bis(ethylenediamine) in its name.

S. The oxidation state of the central metal ion is given by a Roman numeral (in
parentheses) only if the metal ion can have more than one state, as in the com
pound named in rule I.

6. If the complex ion is an anion, we drop the ending of the metal name and add
-ate. Thus, the name for K[Pt(NH3)CJ5] is
potassium amminepentachloroplatinate(IV)

Metal

Name in Anion

Iron
Copper
Lead
Silver
Gold
Tin

Ferrate
Cuprate
Plumbate
Argentate
Aurate
Stannate

(d) This compound consists of two different complex ions. In the cation. hexaammine is
six NH3 and cobalt(/I1) is Co3+, so the cation is [Co(NH3)613+.The 3+ charge is the sum
of 3+ for Co3+ and 0 for six NH3. In the anion, tetrachloro is four CI-, andferrare(I11)
is Fe3+, so the anion is [FeCI4J-. The 1- charge is the sum of 3+ for Fe3+ and 4- for
four Cl". In the neutral compound, one 3+ cation is balanced by three 1- anions:
[CO(I\'H3)6][FeCI4h
Check Reverse the process to be sure you obtain the name or formula asked for in the
problem.

FOLLOW-UP PROBLEM 23,3

(a) What is the name of [Cr(H20)sBr]CI2?

(b) What is the formula of barium hexacyanocobaitate(llJ)?

A Historical Perspective: Alfred Werner and Coordination Theory

The substances we now call coordination compounds had been known for almost
200 years when the young Swiss chemist Alfred Werner began studying them in
the 1890s. He investigated a series of compounds such as the cobalt series shown
in Table 23.10, each of which contains one cobalt(III) ion, three chloride ions,
and a given number of ammonia molecules. At the time, which was 30 years
before the idea of atomic orbitals was proposed, no structural theory could explain
how compounds with similar, even identical, formulas could have widely differ
ent properties.
Werner measured the conductivity of each compound in aqueous solution to
determine the total number of ions that became dissociated. He treated the solu
tions with excess AgN03 to precipitate released CI- ions as AgCl and thus deter
mine the number of free CI- ions per formula unit. Previous studies had
established that the NH3 molecules were not free in solution. Werner's data, sum
marized in Table 23.10, could not be explained by the accepted, traditional for
mulas of the compounds. Other chemists had proposed "chain" structures, like
those of organic compounds, to explain such data. For example, a proposed struc
ture for [Co(NH3)6]CI3 was
N H3

-C1
C o-

NH}- CI

NH3-NH3-NH3-NH3-CI

However, these models proved inadequate.

Werner's novel idea was the coordination complex, a central metal ion sur
rounded by a constant total number of covalently bonded molecules and/or
anions. The coordination complex could be neutral or charged: if charged, it com
bined with oppositely charged counter ions. in this case CI-. to form the neutral
compound.

'MNlf!

[II Some Coordination

Compounds of Cobalt Studied by

Werner
Werner's Data'"
Traditional

Total Free

Modern
Formula

Charge of
Ions

CI-

CoCI3,6NH3

CoCly5NH3
CoCI3'4NH3
CoCI33NI-I3

"Molesper mole of compound.

Formula
[Co(NH3)lilCI3
[Co(NH3)sCI]Ch
[Co(NH3)4CiZJCI
[Co(NH3hCI31

Complex Ion
3+
2+
1+

21.4 Coordination
Compounds
Chapter 23 The Transition
Elements and
Their Coordination Compounds

102

Werner proposed two types of valence, or combining ability, for metal ions.
Primary valence, now called oxidation state, is the positive charge on the metal
ion that must be satisfied by an equivalent negative charge. In Werner's cobalt
series, the primary valence is +3, and it is always balanced by three Cl" ions.
These anions can be bonded covalently to Co as part of the complex ion and/or
associated with it as counter ions. Secondary valence, now called coordination
number, is the constant total number of connections (anionic or neutral ligands)
within the complex ion. The secondary valence in this series of Co compounds is 6.
As you can see, Werner's data are satisfied if the total number of ligands
remains the same for each compound, even though the numbers of CI- ions and
NH3 molecules in the different complex ions vary. For example, the first com
pound, [CO(NH3)6]CI3,has a total of four ions: one [Co(NH3)6]3+ and three 0-.
All three Cl" ions are free to form AgCl. The last compound, [Co(NH3hCI3],
contains no separate ions.
Surprisingly, Werner was an organic chemist, and his work on coordination
compounds, which vi..rtuallyrevolutionized his contemporaries' understanding of
chemical bonding, was his attempt to demonstrate the unity of chemistry. For
these pioneering studies, especially his prediction of optical isomerisrn (discussed
next), Werner received the Nobel Prize in chemistry in 1913.

Isomerism in Coordination Compounds

Isomers are compounds with the same chemical formula but different properties.
We discussed many aspects of isomerism in the context of organic compounds in
Section 15.2; it may be helpful to review that section now. Figure 23.10 presents
an overview of the most common types of isomerism in coordination compounds.

iil:Ji ilii![.'lmportant

types of
isomerism in coordination
compounds.

ISOMERS

same chemicalformula,but
differentproperties

ConstltuUonal(structural) isomers
Atoms connecteddifferently
Coordination isomers
Ligandand counter-ion
exchange

Stereoisomers
DIfferentspallal arrangement

Linkage isomers

Geometric (cis-trans)
isomers (diastereomers)

Optical isomers
(enantlomers)

Differentdonor atom

Differentarrangement
around metal ion

Nonsuperimposable
mirror images

Constitutional Isomers: Same Atoms Connected Differently Two compounds

with the same formula, but with the atoms connected differently, are called con
stitutional (structural) isomers. Coordination compounds exhibit the following
two types of constitutional isomers: one involves a difference in the composition
of the complex ion, the other in the donor atom of the ligand.
1. Coordination isomers occur when the composition of the complex ion
changes but not that of the compound. One way this type of isomerism occurs
is when ligand and counter ion exchange positions, as in [Pt(NH3)4Cl2](N02h
and [Pt(NH3MN02h]C12. In the first compound, the CC ions are the ligands, and
the N02 - ions are counter ions; in the second, the roles are reversed. Another
way that this type of isomerism occurs is in compounds of two complex ions in
which the two sets of ligands in one compound are reversed in the other, as in
[Cr(NH3)r,][Co(CN)r,] and [Co(NH3)(i][Cr(CN)6]; note that NH3 is a ligand of
Cr3+ in one compound and of Co3+ in the other.

102
310

2. Linkage isomers occur when the composition of the complex ion remains
the same but the attachment of the ligand donor atom changes. Some ligands can
bind to the metal ion through either of two donor atoms. For example, the nitrite
ion can bind through a lone pair on either the N atom (nitro, 02N:) or one of the
o atoms tnitrito, ONO:) to give linkage isomers, as in the orange compound pen
taamminenitrocobalt(lII) chloride [Co(NH3)s(NOz)]Ch (below left) and its red
linkage isomer pentaamminenitritocobalt(Ill) chloride [Co(NH3h(ONO)]Clz
(below right):

Nitro isomer

Nitrito isomer

Another example is the cyanate ion, which can attach via a lone pair on the
o atom (cyanate, NCO:) or the N atom (isocyanato, OCN:); the thiocyanate ion
behaves similarly, attaching via the S atom or the N atom:
-o, ~:

]-N:
./
[ :9.
nitrite

AnticancerGeometric Isomers In the

mid-I'J60s, Barnett Rosenberg and his
colleagues found that cis-[Pt\NH3)2CI2]
(cisplatin) was a highly effective anti
tumor agem, Thi, compound and several
closely related platinum(lI) complexes
are still among the most effective treat
ments for certain types of cancer. The
geometric isomer, trons-[Pt,NH3hCI2],
however, has no antitumor effect. Cis
platin may work by lying within the can
cer cell's DNA double helix, such that
a donor atom on each strand replaces a
Cl" ligand and binds the plarinum(lI)
strongly, preventing DNA replication
(Section 15.6).

[O=C=N:]cyanate

[:S=C=N:J
thiocyanate

Stereoisomers: Different Spatial Arrangements of Atoms Stereoisomers are

compounds that have the same atomic connections but different spatial arrange
ments of the atoms. The two types we discussed for organic compounds, called
geometric and optical isomers, are seen with coordinarion compounds as well:
I. Geometric isomers (also called cis-trans isomers and, sometimes,
diastereomersy occur when atoms or groups of atoms are arranged differently in
space relative to the central metal ion. For example, the square planar
[Pt(NH3hClz] has two arrangements, which give rise to two different compounds
(Figure 23.11A). The isomer with identical ligands next to each other is cis
diarnminedichloroplatinumrll), and the one with identical ligands across from
each other is Irans-diamminedichloroplatinum(II); their biological behaviors are
remarkably different.
Octahedral complexes also exhibit cis-trans isomerism
(Figure 23.11B). The cis isomer of the [Co(NH])4Ch]+ ion has the two CI- li
gands next 10 each other and is violet, whereas the trans isomer has these two
ligands across from each other and is green.
2. Optical isomers (also called enantiomersi occur when a molecule and its
mirror image cannot be superimposed (see Figures 15.8 to 15.10. pp. 627-628).
Unlike other types of isomers, which have distinct physical properties, optical iso
mers are physically identical in all ways but one: the direction ill which they rotate
the plane of polarized light. Octahedral complex ions show many examples of
optical isomerism, which we can observe by rotating one isomer and seeing if it
is superimposable on the other isomer (its mirror image). For example, as you
can see in Figure 23.I2A, the two structures (I and II) of [Co(enhClz]+, the
cis-dichlorobis(ethylenediamine)cobalt(III) ion. are mirror images of each other.
Rotate structure I 1800 around a vertical axis, and you obtain III. The CI- li-

102
510

23.4 Cooridination Compounds

Chapter 23 The Transition Elements and Their Coordination Compounds

102

Figure 23.11Geometric (cis-trans)

isomerism.A, The cis and trans isomers
of the square planar coordination com
pound [Pt(NH3bCI21B. , The cis and
trans
isomers of the octahedral complex ion
[Co(NH3)4CI2r. The colored shapes
rep resent the actual colors of the
species.

gands of III match those of II, but the en ligands do not: II and III (rotated I) are
not superimposable: therefore. they are optical isomers. One isomer is designated
d-[Co(enhCI2]+ and the other is 1-[Co(enhCI21+, depending on whether it rotates
polarized light to the right (d- for "dextro-") or to the left (/- for "levo-"). (The
d- or 1- designation can only be determined experimentally, not by examination
of the structure.) In contrast, as shown in figure 23.12B, the two structures of the
trans-dichlorobis(ethylenediamine)cobalt(III) ion are nor optical isomers: rotate 1
90 around a vertical axis and you obtain III, which is superimposable on U.

-4-=>
N
N .

I ,..

CICI.

"""'1"111

Co

't.\\\\\""~
't.\\\"...........

N/ i "'CI
N

CI/

CI,

i "N

CI/I~N

N
II

.' N

IIIIJIIICO*\\\\'~\..

..l.l..l.1,',111.

Co

N",I,c,

not same as

Co
CI/i~N

I
N

HI

N
II

N
same as

III

Figure 23.12 Optical isomerism in an octahedral complex ion.

A, Structure I and its mirror image, structure II, are optical isomers of
cis-[Co(en)2CI21+R. otating structure I gives structure III, which is
not the same as structure II. (The curved wedges represent the
bidentate

ligand ethylenediamine, H2N-CH2-CH2-NH2.)

B, The trans isomer
does not have optical isomers. Rotating structure I gives III, which is
identical to II. the mirror image of I.

Br~'"
~"'''Pt\'''~

/'

(a)

H3N

...N.. Ha
..'NHa

-,Sr

HaN...
'~""Pt\"~'~

/' -,Sr

Sr

trans

cis

Mirror
3+ :
~,"~"N
N
a+
...".....
N.
.N
N
N,..
""'Cr"'" )
N....... . "'N
N....... .

I
( <s:I

I .'
I

"'N
'N

N~
not the sameas
N

~
(b)

(N.""'.CrI~_"".,

N....... . 7'N
N'

3+

SAMPLE PROBLEM 23.4 Determining the Type of Stereoisomerism

Problem Draw all stereoisomers for each of the following and state the type of isomerism:
(a) [Pt(NH3hBrzl (square planar)
(b) [Cr(enhJ3+ (en = H2NCHzCHiNH2)
Plan We first determine the geometry around each metal ion and the nature of the ligands.
If there are two different ligands that can be placed in different positions relative to each
other, geometric (cis-trans)isomerism occurs. Then, we see whether the mirror image of
an isomer is superimposable on the original. If it is not, optical isomerism occurs.
Solution (a) The Pt(Il) complex is square planar. and there are two different rnonoden
late ligands. Each pair of ligands can lie next to or across from each other (see structures
in margin). Thus, geometric isomerism occurs. Each isomer is superimposable on its mir
ror image, so there is no optical isomerism.
(b) Ethylenediamine (en) is a bidentate ligand. The C~+ has a coordination number of 6
and an octahedral geometry. like CoH. The three bidentate ligands are identical, so there
is no geometric isomerism. However, the complex ion has a nonsuperimposable mirror
image (see structures in margin). Thus, optical isomerism occurs.

FOLLOW-UP

PROBLEM

[Co(NH3hCen)CI~1+ion?

B.4

What stereoisomers, if any, are possible for the

Coordination compounds consist of a complex ion and charge-balancing counter ions.

The complex ion has a central metal ion bonded to neutral and/or anionic ligands.
which have one or more donor atoms that each provide a lone pair of electrons. The
most common geometry is octahedral (six ligand atoms bonding). Formulas and names
of coordination compounds follow systematic rules. Werner established the structural
basis of coordination compounds. These compounds can exhibit constitutional iso
merism (coordination and linkage) and stereoisomerism (geometric and optical).

23.5 THEORETICAL BASIS FOR THE BONDING AND

PROPERTIES OF COMPLEXES
In this section, we consider models that address. in different ways, several key
features of complexes: how metal-ligand bonds form, why certain geometries are
preferred, and why these complexes are brightly colored and often paramagnetic.
As you saw with covalent bonding in other compounds (Chapter 11), more than
one model is often needed to tell the whole story.

Application of Valence Bond Theory to Complex Ions

Valence bond (VB) theory, which helped explain bonding and structure in main
group compounds (Section 11.1), is also used to describe bonding in complex
ions. In the formation of a complex ion, the filled ligand orbital overlaps the
empty metal-ion orbital. The ligand (Lewis base) donates the electron pair. and

the metal iOI1 (Lewis acid) accepts it to form one of the covalent bonds of {he
complex ion (Lewis adduct) (Section 18.9). Such a bond, in which one atom in
the bond contributes both electrons, is called a coordinate
covalent bond,
although, once formed, it is identical to any covalent single bond. Recall that the
VB concept of hybridization proposes the mixing of particular combinations of s,
p, and d orbitals to give sets of hybrid orbitals, which have specific geometries.
Similarly, for coordination compounds, the model proposes that the number and

type of metal-ion hybrid orbitals occupied by ligand lone pairs determine the
geometry of the complex ion. Let's discuss the orbital combinations that lead to
octahedral,

square planar, and tetrahedral geometries.

23.5

102

Theoretical

Basis for 23
the The
Bonding
and
Chapter
Transition

3d :- - - --

I tit It L

Properties
Elements

of Complexes
and
Their Coordination

--is- - - - 4P- --I

lgLl

I IJ

Cr3+

3d
[Cr(NH3)sJ3+

Compounds

102

Figure23.13 Hybrid orbitals and

bonding in the octahedral [Cr(NHl)6]H
ion.

A. VB depiction of the Cr(NH3l6s+ion.

B.
mixing of two 3d, one 4s, and three 4p
orbitals in c(3+ to form six d2sps hybrid
orbitals, which are filled with Six NHs
lone pairs (red).

d2sp3

Octahedral Complexes The hexaamminechromium(III) ion, [Cr(NH3)6]3+. illus

trates the application of VB theory to an octahedral complex (Figure 23.13). The
six lowest energy empty orbitals of the Cr3+ ion-two 3d, one 4s, and three 4p
mix and become six equivalent d2sp3 hybrid orbitals that point toward the cor
ners of an octahedron.* Six NH3 molecules donate lone pairs from their nitrogens
to form six metal-ligand bonds. The three unpaired 3d electrons of the central
CrH ion ([ArJ 3d3), which make the complex ion paramagnetic, remain in unhy
bridized orbitals.

Square Planar Complexes Metal ions with a dB configuration usually form square
planar complexes (Figure 23.14). In the [Ni(CN)4]2- ion, for example, the model
proposes that one 3d, one 4s, and two 4p orbitals of Ni2+ mix and form four dsp2
hybrid orbitals, which point to the comers of a square and accept one electron
pair from each of four CN- ligands.
A look at the ground-state electron configuration of the Ni2+ ion, however,
raises a key question: how can the Ni2+ ion ([Ar] 3d8) offer an empty 3d orbital
for accepting a lone pair, if its eight 3d electrons lie in three filled and two half
filled orbitals? Apparently, in the d8 configuration of N?+, electrons in the half
filled orbitals pair up and leave one 3d orbital empty. This explanation is
consistent with the fact that the complex is diamagnetic (no unpaired electrons).
Moreover, it requires that the energy gained by using a 3d orbital for bonding in
the hybrid orbital is greater than the energy required to overcome repulsions from
pairing the 3d electrons.
'Note the distinction between the hybrid-orbital designation here and that for octahedral mol
ecules like SFa.The designation gives the orbitals in energy order within a given n value. In the
[Cr(NH:J6J3+complex ion, the d orbitals have a lower n value than the s and p orbitals, so
the
hybrid orbitals are d~sp3. For the orbitals in SFs, the d orbitals have the same n value as the
s
and p, so the hybrid orbitals are sp3d2.

Figure23.14 Hybrid

orbitals and bonding

in the square planar [Ni(CN).]l- ion.

3d
[Ni(CN)412-

A, VB depiction of [Ni(CN).J2-. B. Two

lone 3d electrons pair up and free one
3d orbital for hybridization with the 4s
and two of the 4p orbitals to form four
dSp2 orbitals, which become occupied
with Jonepairs (red) from four CNligands.
4p

Figure 11.15Hybrid orbitals and bonding

in the tetrahedral [In(OH)411-ion.
A, VB depiction of [Zn(oH).f-. B, Mixing
one 45 and three 4p orbitals gives four

'r

hybrid orbitals available for accepting

lone pairs (red) from OH ligands.

mi

Sp3

40

1tJ,lulnltJ,ItJ,1 IHlt.1.IHIHI
3d

5,73

B [Zn(OH)4l2-

Tetrahedral Complexes Metal ions that have a filled

d sublevel, such as Zn2+

([Ar] 3dIO), often form tetrahedral complexes (Figure 23.15). For the complex
ion [Zn(OH)4f-, for example, VB theory proposes that the lowest available Zn2+
orbitals-one 4s and three 4p-mix to become four Sp3 hybrid orbitals that point
to the comers of a tetrahedron and are occupied by four lone pairs, one from each
of four OH- ligands.

Crystal Field Theory

The VB model is easy to picture and rationalizes bonding and shape, but it treats
the orbitals as little more than empty "slots" for accepting electron pairs. Conse
quently, it gives no insight into the colors of coordination compounds and some
times predicts their magnetic properties incorrectly. In contrast to the VB
approach, crystal field theory provides little insight about metal-ligand bonding
but explains color and magnetism clearly. To do so, it highlights the effects all
the d-orbital energies of the metal ion as the ligands approach. Before we dis
cuss this theory, let's consider what causes a substance to be colored.

What Is Color? White light is electromagnetic radiation consisting of all wave

Blue

560

Figure 23.16 An artist's wheel.

Colors,
with approximate wavelength ranges (in
nm), are shown as wedges. Complemen

tary colors, such as red and green, lie

opposite

each other.

lengths ()\) in the visible range (Section 7.1). It can be dispersed into a spectrum
of colors, each of which has a narrower range of wavelengths. Objects appear
colored in white light because they absorb certain wavelengths and reflect or
transmit others: an opaque object reflects light, whereas a clear one transmits it.
The reflected or transmitted light enters the eye and the brain perceives a color.
If an object absorbs all visible wavelengths, it appears black; if it reflects all, it
appears white.
Each color has a complementary color. For example, green and red are com
plementary colors. A mixture of complementary colors absorbs all visible wave
lengths and appears black. Figure 23.16 shows these relationships on an artist's
color wheel, where complementary colors appear as wedges opposite each other.
An Object has a particular color for one of two reasons:
It reflects (or transmits) light of that color. Thus, if an object absorbs all wave
lengths except green, the retlected (or transmitted) light enters our eyes and is
interpreted as green.
It absorbs light of the complementary color. Thus, if the object absorbs only
red, the complement of green, the remaining mixture of reflected (or transmit
ted) wavelengths enters our eyes and is interpreted as green also.
Table 23.11 lists the color absorbed and the resulting color perceived. A familiar
example of this phenomenon results in the seasonal colors of deciduous trees. In
the spring and summer, leaves contain high concentrations of the photosynthetic
pigment chlorophyll and lower concentrations of other pigments called xantho
phylls. Chlorophyll absorbs strongly in the blue and red regions, reflecting mostly
green wavelengths into your eyes. In the fall, photosynthesis slows, so the leaf
no longer makes chlorophyll. Gradually, the green color fades as the chlorophyll
decomposes, revealing the xanthophylls that were present all along but masked

102

23.S Theoretical Basisfor the Bonding and Properties of Complexes

Chapter 23 The Transition Elements and Their Coordination Compounds

Id~rti!11Relation Between
Absorbed Color
Violet
Blue
Blue-green
Yellow-green
Yellow
Orange
Red

1029

Absorbed and Observed Colors

A. (nm)

Observed Color

400
~50
~90
570
580
600
650

A. (nm)

560

Green-yellow
Yellow
Red
Violet
Dark blue
Blue
Green

600

620
410
430
450
520

by the chlorophyll. Xanthophylls absorb green and blue strongly. reflecting the
bright yellows and reds of autumn (see photo).

Foliage changing color in autumn.

Splitting of d Orbitals in an Octahedral Field of Ligands The crystal field model

explains that the properties of complexes result from the splitting of d-orbital
energies. which arises from electrostatic interactions between metal ion and li
gands. The model assumes that a complex ion forms as a result of electrostatic
attractions between the metal cation and the negative charge of the ligands. This
negative charge is either partial, as in a polar neutral ligand like NH), or full, as in
an anionic ligand like CI-. The ligands approach the metal ion along the mutually
perpendicular x, y, and z axes, which minimizes the overall energy of the system.
Picture what happens as the ligands approach. Figure 23.17A shows six li
gands moving toward a metal ion to form an octahedral complex. Let's see how
the various d orbitals of the metal ion are affected as the complex forms. As the
ligands approach, their electron pairs repel electrons in the five d orbitals. In the
isolated metal ion, the d orbitals have equal energies despite their different ori
entations. In the electrostatic field of ligands. however. the d electrons are repelled
unequally because their orbitals hare different orientations. Because the ligands
move along the x, y, and::: axes, they approach directly toward the lobes of the
dx'_y' and d:, orbitals (Figure 23.17B and C) but between the lobes of the
d.\'),. d.v:, and d,,: orbitals (Figure 23.17D to F). Thus, electrons in the d.<2_y2
and dz' orbitals experience stronger repulsions than those in the d.,)., d,-::.and dy:
orbitals.
z

iil:Ji iiii! fA The five d orbitals in an

dz"

dyz

octahedral field of ligands. The direction

of ligand approach influences the
strength of repulsions of electrons in the
five metal d orbitals. A, We assume that
ligandSapproach a metal ion along the
three linear axes in an octahedral orienta
tion. Band C, Lobes of the d_y' and dz'
orbitals lie directly in line with the ap
proaching ligands, so repulsions are
stronger. 0 to F. Lobes of the dxy, dxz, and
dyz orbitals lie between the approaching
ligands, so repulsions are weaker.

m.;: i Iii!!:' Splitting of d-orbital

eg

//lR:,--,

energies by an octahedral field of

ligands. Electrons in the d orbitals of the
free
metal ion experience an average net re
pulsion in the negative ligand field that

/00000/""

form the t2g set. are repelled less than

increases

all

d-orbital

energies.

OODOO

Electrons
in the dxy. dyz. and dxz orbitals. which

t2g

,/

"000

'

those in the dx'-y' and dz' orbitals. which

form the eg set. The energy difference
be tween these two sets is the crystal
field
splitting energy. A.

Averagepotentialenergy
of 3d orbnals raisedin

3d orbitalsin free ion

Weak-field
ligands

eg

[ILJ

.-....--.,---,

t2g

eg[]J

{!,

{!,

11' 11' 11' It!

t2g
[Cr(H20)612+

octahedralligand field

~~~

3d orbilal splittingin
octahedralligandfield

An energy diagram of the orbitals shows that all five d orbitals are higher in
energy in the forming complex than in the free metal ion because of repulsions
from the approaching ligands, but the orbital energies split, with two d orbitals
higher in energy than the other three (Figure 23.18). The two higher energy

Strong-field
ligands

!!.

IH 11' 11' I
[Cr(CN)s14-

Figure 23.19The effect of the ligand

on splitting energy. Ugands interacting

strongly with metal-ion d orbitals, such as

eN produce a larger A than those inter
acting weakly, such as H20.

orbitals are called eg orbitals, and the three lower energy ones are Izg orbitals .
(These designations refer to features of the orbitals that need not concern us here.)
The splitting of orbital energies is called the crystal field effect. and the dif
ference in energy between the eg and l2g sets of orbitals is the crystal field split
ting energy (~). Different ligands create crystal fields of different strength and,
thus, cause the d-orbital energies to split to different extents. Strong-field ligands
lead to a larger splitting energy (larger 6); weak-field ligands lead to a smaller
splitting energy (smaller 6). For instance, H20 is a weak-field ligand, and CN
is a strong-field ligand (Figure 23.19). The magnitude of 6 relates directly to the
color and magnetic properties of a complex.

Explaining the Colors of Transition Metals The remarkably diverse colors of

coordination compounds are determined by the energy difference (6) between the
t2q and eM orbital sets in their complex ions. When the ion absorbs light in the
visible range, electrons are excited (rjump'') from the lower energy l2g level to
the higher eg level. Recall that the difference between two electronic energy lev
els in the ion is equal to the energy (and inversely related to the wavelength) of
the absorbed photon:
AE.1oc"on

Epholon

hv

hcA

The substance has a color because only certain wavelengths of the incoming white
light are absorbed.
Consider the [Ti(1-120)6]3+ ion. which appears purple in aqueous solution
(Figure 23.20). Hydrated Ti3+ is a d' ion. with the d electron in one of the three
e-jumpsto

higher level~ L.!..LJe g

400

500

600

700

Wavelength(nm)

figure 2l.20 The color of [Ti(H10)6]H. A, The hydrated n3+ ion is

purple in aqueous solution. B, An absorption spectrum shows that in
coming wavelengths corresponding to green and yellow light are ab-

Incoming)..

Absorbed)"

Transmittedx

c
sorbed, whereas other wavelengths are transmitted. C, An orbital
dia gram depicts the colors absorbed in the excitation of the d
electron to the higher level.

103

23.5

Transition
Elements and
Their Coordination Compounds
Theoretical Chapter
Basis for 23
theThe
Bonding
and Properties
of Complexes

lower energy t28 orbitals. The energy difference (ll.) between the t28 and eg orbitals
in this ion corresponds to the energy of photons spanning the green and yellow
range. When white light shines on the solution, these colors of light are absorbed,
and the electron jumps to one of the e.~orbitals. Red, blue, and violet light are
transmitted, so the solution appears purple.
Absorption spectra show the wavelengths absorbed by a given metal ion with
different ligands and by different metal ions with the same ligand. From such
data, we relate the energy of the absorbed light to the ll. values, and two impor
tant observations emerge:
1. For a given ligand, [he color depends on the oxidation state of the metal ion.
A solution of [V(H20)(;f+ ion is violet, and a solution of [V(H20)(;]3+ ion is
yellow (Figure 23.21A).
2. For a given metal ion, the color depends all the ligand. Even a single ligand
substitution can have a major effect on the wavelengths absorbed and. thus,
the color, as you can see for two Cr3+ complex ions in Figure 23.2IB.
The second observation allows us to rank ligands into a spectrochemical
series with regard to their ability to split d-orbital energies. An abbreviated series,
moving from weak-field ligands (small splitting, small ~) to strong-field ligands
(large splitting, large ~), is shown in Figure 23.22. Using this series. we can pre
dict the relative size of ll. for a series of octahedral complexes of the same metal
ion. Although it is difficult to predict the actual color of a given complex, we can
determine whether a complex will absorb longer or shorter wavelengths than other
complexes in the series.

SAMPLE PROBLEM

Figure 23.21Effectsof the metal oxida

tion state and of ligand identity on
color. A, Solutions of [V(H20)612+!Jeft)
and [V(H20)613+(right) ions have different
col ors. B, A change in even a single
ligand can influence the color. The
[Cr(NH3)613+
ion is Yellow-orange (left); the
[Cr(NHalsCtf+ ion is purple (right).

n.s RankingCrystal Field Splitting Energies

for Complex Ions of a Given Metal

Problem Rank the ions [fi(H10)6]3+,[1'i(NH3)6J3+a,nd [1'i(CN)6J3-in terms of the
rel
ative value of .1 and of the energy of visible light
absorbed.
Plan The formulasshow that titanium's oxidationstate is +3 in the three ions. From
Fig ure 23.22, we rank the ligands in terms of crystal field strength: the stronger the
ligand, the greater the splitting, and the higher the energy of light absorbed.
Solution The ligand fieldstrength is in the orderCN- > NH3 > H20, so the
relativesize
of ~ and energy of light ahsorbed
is
1'i(CN)63- > Ti(NH3)63+ > 1'i(H20)63+

FOLLOW-UP PROBLEM 21.5 Which complex ion absorbs visible light of higher
energy, [V(H20)6J3+ or [V(NH3)6]3+?

WEAKER FIELD

STRONGER FIELD

SMALLER!>.

LARGER!>.

LONGER)"

SHORTER),

ill} ilJlfllThe spectrochemical series.

As the crystal field strength of the ligand increases,

the splitting energy (..l.) increases. so shorter wavelengths (A) of light must be absorbed to excite
electrons. Water is usually a weak-field ligand.

10

~
~

Animation: Vanadium Reduction

Online Learning Center

Strong-field ligand
Low-spincomplex

-rr

Epairing < l!.

Weak-field ligand
High-spincomplex
No field
Maximumnumberof
unpairedelectrons

Eprunng > l!.

eg

[ill]

.\

l!.

ltltltltltl

12g 1

A Free Mn2+ion

B [Mn(H20)6]2+

tit

t29 I tJ, 1 tJ, 1

[Mn(CN)6]4-

Figure 23.23 High-spin and low-spin complex ions of Mnl+. A, The free Mn2+ ion has five
unpaired electrons. S, Bonded to weak-field ligands (smaller ~), Mn2+ stili has five unpaired
electrons (high spin complex). C, Bonded to strong-field ligands (larger .1), Mn2+ has only one
unpaired electron (low-spin complex).

High spin:
weak-field
ligand

Low spin:
strong-field
ligand

IT]

IT]

iii} ithlU

Orbital occupancy for

high-spin and low-spin complexes of d4
through d7 metal ions.

Explaining the Magnetic Properties of Transition Metal Complexes The splitting

of energy levels influences magnetic properties by affecting the number of
unpaired electrons in the metal ion's d orbitals. Based on Hund's rule, electrons
occupy orbitals one at a time as long as orbitals of equal energy are available.
When all lower energy orbitals are half-filled. the next electron can
enter a half-filled orbital and pair up by overcoming a repulsive pairing energy
(Epairing), or
enter an empty, higher energy orbital by overcoming the crystal field splitting
energy (6.).
Thus, the relative sizes ofEpo;";IIR and 6. determine Theoccupancy of Thed orbitals.
The orbital occupancy pattern, in turn, determines the number of unpaired elec
trons and, thus, the paramagnetic behavior of the ion.
As an example, the isolated Mn2+ ion ([AI'] 3d5) has five unpaired electrons
in 3d orbitals of equal energy (Figure 23.23A). In an octahedral field of ligands,
the orbital energies split. The orbital occupancy is affected by the ligand in one
of two ways:
Weak~field ligands and high-spill complexes. Weak-field ligands, such
as H:P in [Mn(H20)6f+, cause a small splitting energy, so it takes less
energy for d electrons to jump to the eg set than to pair up in the t2/1 set.
Therefore, the d electrons remain unpaired (Figure 23.23B). Thus, with weakfield ligands, the
pairing energy is greater than the splitting energy (Epairing > 6.); therefore,
the number of unpaired electrons in the complex ion is the same as in the free
ion. Weak-field ligands create high-spin complexes, those with the maximum
num
ber of unpaired electrons.
Strong-field ligands and low-spin complexes. In contrast, strong-field ligands,
such as CN- in [Mn(CN)6]4-, cause a large splitting of the d-orbital energies,
so it takes more energy for electrons to jump to the eg set than to pair up in
the t28 set (Figure 23.23C). With strong-field ligands, the pairing energy is
smaller than the splitting energy (Ep.iring < t.); therefore, the number of
unpaired electrons in the complex ion is less than in the free ion. Strong-field
ligands create low-spin complexes, those with fewer unpaired electrons.
Orbital diagrams for the dl through d9 ions in octahedral comrlexes show
that both high-spin and low-spin options are possible only for ct, d , d6, and d7
ions (Figure 23.24). With three lower energy (2~ orbitals available, the dl, d2, and
d3 ions always form high-spin complexes because there is no need to pair up.
Similarly, d8 and d9 ions always form high-spin complexes: because the t28 set is
filled with six electrons, the two eg orbitals mUST have either two (d8) or one (d9)
unpaired electron.

Theoretical Chapter
Basis for 23
the The
Bonding
and Properties
Transition
Elements ofandComplexes
Their Coordination

21.5

103

103

Compounds

SAMPLE

PROBLEM

13.6 Identifying

Complex Ions as High Spin or Low Spin

Problem Iron(1I) forms an essential complex in hemoglobin. For each of the two octahe
dral complex ions [Fe(H20)612+ and [Fe(CN)6)4-, draw an orbital splitting diagram, pre
dict the number of unpaired electrons, and identify the ion as low spin or high spin.
Plan The Fe2+ electron configuration gives us the number of d electrons, and the spec
trochemical series in Figure 23.22 shows the relative strengths of the two ligands. We draw
the diagrams. separating the t2~ and eg sets by a greater distance for the strong-field li
gand. Then we add electrons, noting that a weak-field ligand gives the maximum number
of unpaired electrons and a high-spin complex, whereas a strong-field ligand leads to elec
tron pairing and a low-spin complex.
Solution Fe2+ has the [Ar) 3et configuration. According to Figure 23.22, H20 produces
smaller splitting than CN-. The diagrams are shown in the margin. The [Fe(H20)6f+ ion
has four unpaired electrons (high spin), and the [Fe(CN)6)4- ion has no unpaired
electrons (low spin).
Comment 1. H20 is a weak-field ligand, so it almost always forms high-spin complexes.
2. These results are correct, but we cannot confidently predict the spin of a complex with
out having actual values for!!' and Epairing'
3. Cyanide ions and carbon monoxide are
highly toxic because they interact with the iron cations in proteins.

PROBLEM B.6 How many unpaired electrons do you expect for

[Mn(CN)6)3-? Is this a high-spin or low-spin complex ion?

FOLLOW-UP

Crystal Field Splitting in Tetrahedral and Square Planar Complexes Four ligands
around a metal ion also cause d-orbital splitting, but the magnitude and pattern
of the splitting depend on whether the ligands are in a tetrahedral or a square pla
nar arrangement.

Tetrahedral complexes. With the ligands approaching from the comers of a

tetrahedron, none of the five d orbitals is directly in their paths (Figure 23.25).
Thus, splitting of d-orbital energies is less in a tetrahedra] complex than in an
octahedral complex having the same ligands:
~tetrahedral

<

~octahedral

Minimal repulsions arise if the ligands approach the dAY' dy;:, and d-=: orbitals
closer than they approach the d;:>and d.,'_y2 orbitals. This situation is the
oppo site of the octahedral case, and the relative d-orbital energies are reversed:
the
d,~., d\"=,and de orbitals become higher in energy than the dz1 and
dx'_v2 orbitals. Only high-spin tetrahedral complexes are known because the
magni tude of 6. is so smalL

<,

.?/

~
e-,

Q)

-y

Q)

c:

~
E

Q)

(5

a.

liM'it)fft

000
!!. letrahedral

0 0t

dJ2_y2

dz>

Splitting of d-orbital energies by a tetrahedral field of ligands. Electrons in dxy. dyz,

and d xz orbitals experience greater repulsions than those in dx'-y"' and dz" so the tetrahedral
split ting pattern is the opposite of the octahedral pattern.

[Fe(CN).J4-

[Fe(H2O)6l"+
>Q)

c:
Q)

"iii

ITJe

ITI.!J e

INlt I t I t

2g
2g

INIHIHIt

f
z

>.

D"""

Square planar complexes. The effects of the ligand field in the square pla
nar case are easier to picture if we imagine starting with an octahedral
geometry and then remove the two ligands along the z-axis, as depicted
in Figure 23.26. With no z-axis interactions present, the do2 orbital energy
decreases greatly. and the energies of the other orbitals with a z-axis com
ponent, the de and dp also decrease. As a result, the two d orbitals in
the .ry plane interact most strongly with the ligands. and because the dX2_y2
orbital has its lobes on the axes, its energy is highest. As a consequence
of this splitting pattem, square planar complexes with d8 metal ions, such

d,{'_?

....r..

.--..

f2'

OJ

dxy

""

as [PdCI

1'9" x "E
OJ

(5
n,

D
D D
dZ2

dxz

lin: i liltt.' Splitting of d-orbital

energies by a square planar field of

ligands. In a square planar field. the
energies of dxz. dyz, and
especially dZ2 orbitals decrease
relativeto the octa hedral pattern.

dyz

P-,

are diamagnetic,

with four pairs of d electrons

filling the

four lowest energy orbitals. Thus, as a general rule, square planar com

plexes are low spin.

At this point, a final word about bonding theories may be helpful. As you
have seen in our discussions of several other topics. no one model is satisfactory
in every respect. The VB approach offers a simple picture of bond formation but
does not even attempt to explain color. The crystal field model predicts color and
magnetic behavior beautifully but treats the metal ion and ligands as points of
opposite charge and thus offers no insight about the covalent nature of metal
ligand bonding.
Despite its complexity, chemists now rely on a more refined model. called
ligand field-molecular orbital theory. This theory combines aspects of the previ
ous two models with MD theory (Section 11.3). We won't explore this model
here, but it is a powerful predictive tool. yielding information on bond properties
that result from the overlap of metal ion and ligand orbitals as well as informa
tion on the spectral and magnetic properties that result from the splitting of a
metal ion's d orbitals.
In addition to their important chemical applications, complexes of the transi
tion elements play vital roles in living systems, as the following Chemical Con
nections essay describes.

Valence bond theory pictures bonding in complex ions as arising from coordinate
covalent bonding between Lewis bases (ligands) and Lewis acids (metal ions). Ligand
lone pairs occupy hybridized metal-ion orbitals to form complex ions with character
istic shapes.
Crystal field theory explains the color and magnetism of complexes. As the result
of a surrounding field of ligands. the d-orbital energies of the metal ion split. The mag
nitude of this crystal field splitting energy (tJ.) depends on the charge of the metal ion
and the crystal field strength of the ligand. In turn, j. influences the energy of the pho
ton absorbed (color) and the number of unpaired d electrons (paramagnetism). Strong
field ligands create a large fl and produce low-spin complexes that absorb light of
higher energy (shorter A); the reverse is true of weak-field ligands. Several transition
metals. such as iron and zinc. are essential dietary trace elements that function in
complexes within proteins.

Chapter Perspective
Our study of the transition elements, a large group of metals with many essential
industrial and biological roles, points out once again that macroscopic properties,
such as color and magnetism, have their roots at the atomic and molecular levels.
which in turn have such a crucial influence on structure. In the next, and final. chapter
we explore the core of the atom and learn how we can apply its enormous power.

to Nutritional Science
Transition Metals as Essential Dietary Trace Elements
hemoglobin (Figure B23.1B). the complex is octahedral. with the
fifth Ligandof iron(II) being an N atom from a nearby amino acid
(histidine), and the sixth an 0 atom from either an O2 (shown) or
an H20 molecule.
Hemoglobin exists in two forms, depending on the nature of
the sixth ligand. In the blood vessels of the lungs, where O2 con
centration is high, heme binds O2 to form oxyhemoglobin, which
is transported in the arteries to OTdepleted tissues. At these tis
sues, the O2 is released and replaced by an H20 molecule to form
deoxyhemoglobin. which is transported in the veins back to the
lungs. The H20 is a weak-field ligand, so the d6 ion Fe2+ in de
oxyhemoglobin is part of a high-spin complex. Because of the rel
atively small d-orbital splitting, deoxyhemoglobin absorbs light at
the red (low-energy) end of the spectrum and looks purplish blue,
which accounts for the dark color of venous blood. On the other
hand, O2 is a strong-field ligand. so it increases the splining en
ergy. which gives rise to a low-spin complex. For this reason. oxy
hemoglobin absorbs at the blue (high-energy) end of the spectrum,
which accounts for the bright red color of arterial blood.
The position of the Fe2+ ion relative to the plane of the por
phin ring also depends on this sixth ligand. Bound to Oz, Fe2+ is
;/1 the porphin plane: bound to H20, it moves out of the plane
slightly. This tiny (-60 pm = 6x 10-11 m) change in the position
of Fe2+ on release or attachment of O2 influences the shape of its
globin chain, which in turn alters the shape of a neighboring glo
bin chain, triggering the release or attachment of its 0], and so on
to the other two globin chains. The very survi val of vertebrate life
is the result of this cooperative "teamwork" by the four globin

'ving things consist primarily of water and complex organic

ornpounds of four building-block elements: carbon. oxygen,
ydrogen, and nitrogen (see Figure 2.18. p. 61). All organisms
also contain seven other elements, known as macronutrients be
cause they occur in fairly high concentrations. In order of increas
ing atomic number, they are sodium, magnesium, phosphorus,
sulfur, chlorine, potassium, and calcium. In addition, organisms
contain a surprisingly large number of other elements in much
lower concentrations, and most of these micronutrients. or trace
elements. are transition metals.
With the exception of scandium and titanium. all Period 4
transition elements are essential for organisms. and plants require
molybdenum (from Period 5) as well. The transition metal ion
usually occurs at a bend of a protein chain covalently bonded to
surrounding amino acid groups whose Nand 0 atoms act as li
gands. Despite the structural complexity of biomolecules, the
principles of bonding and d-orbital splitting are the same as in
simple inorganic systems. Table B23.1 (on the next page) is a List
of the Period 4 transition metals known, or thought, to be essential
in human nutrition. In this discussion we focus on iron and zinc.
Iron plays a crucial role in oxygen transport in all vertebrates.
The oxygen-transporting protein hemoglobin (Figure B23.IA)
consists of four folded protein chains called globins, each cradling
the iron-containing complex heme. Heme is a porphyrin, a com
plex derived from a metal ion and the tetradentate ring ligand
known as porphin. lronrll) is centered in the plane of the porphin
ring, forming coordinate covalent bonds with four N lone pairs,
resulting in a square planar complex. When heme is bound in

Figure 823.1 Hemoglobin and the octahedral complex in heme.

A, Hemoglobin consists of four protein chains. each with a bound

heme. (Illustrationby IrvingGeis. Rights owned by Howard
Hughes MedicalInstitute. Not to be used withoutpermission.)e, In
oxyhemo-

(continued)

globin. the octahedral complex in heme has iron(lI)at the center

sur rounded by the four N atoms of the porphinring.a fifthNfrom
histidine (below). and an O2 molecule (above).

1015

CHEMICAL CONNECTIONS

InOr1:un

(continued)

Some Transition Metal Trace Elements in Humans

Biomolecule Containing Element

Function of Biomolecule

Vanadium

Protein (?)

Redox couple in fat metabolism (?)

Chromium

Glucose tolerance factor

Glucose utilization

Manganese

Isocitrate dehydrogenase

Cell respiration

Iron

Hemoglobin and myoglobin

Cytochrome c
Catalase

Oxygen transport
Cell respiration; ATP formation
Decomposition of H202

Cobalt

Cobalamin (vitamin B12)

Development of red blood cells

Copper

Ceruloplasmin
Cytochrome oxidase

Hemoglobin synthesis
Cell respiration; ATP formation

Zinc

Carbonic anhydrase
Carboxypeptidase A
Alcohol dehydrogenase

Elimination of CO2
Protein digestion
Metabolism of ethanol

Element

chains because it allows hemoglobin to pick up O2 rapidly from

the lungs and unload it rapidly in the tissues.
Carbon monoxide is highly toxic because it binds to the Fe2+
ion in heme about 200 times more tightly than O2 thereby
elimi
nating the heme group from functioning in the circulation. Like
O2 CO is a strong-field ligand and produces a bright red,
"healthy" look in the individual. Because heme binding is an equi
librium process, CO poisoning can be reversed by breathing ex
tremely high concentrations of O2, which effectively displaces CO
from the heme:
heme-CO

+ O2

herne+-O,

electron density from the 0- H bonds, the ZnH makes the

H20 acidic enough to lose a proton. In the rate-determining step,
the re sulting bound OH- ion attacks the partially positive C
atom of CO2 much more vigorously than could the lone pair of a
free wa ter molecule: thus, the reaction rate is higher. One reason
the Cd2+ ion is toxic is that it competes with Zn2+ for fitting into
the car bonic anhydrase active site.

+ CO

Porphin rings are among the most common biological li

gands. Chlorophyll, the photosynthetic pigment of green plants, is
a porphyrin with Mg2+ at the center of the porphin ring, and vita
min BI2 has CoH at the center of a very similar ring system.
Heme itself is found not only in hemoglobin. but also in proteins
called cytochromes that are involved in energy metabolism (see
Chemical Connections, pp. 947-948).
The zinc ion occurs in many enzymes, the protein catalysts of
cells (see Chemical Connections, pp. 709-710). With its dIU con
figuration. Zn2+ has a tetrahedral geometry. typically with the N
atoms of three amino acid groups at three of the positions. and the
fourth position free to interact with the molecule whose reaction is
being catalyzed (Figure B23.2). In every case studied, the ZnH
ion acts as a Lewis acid, accepting a lone pair from the reactant as
a key step in the catalytic process. Consider the enzyme carbonic
anhydrase. which catalyzes the essential reaction between H20
and CO2 during respiration:
CO2(g)

+ H20(l)

H+(aq)

+ HCO, -(aq)

The Zn2+ ion at the enzyme's active site binds three histidine N
atoms and the H20 reactant as the fourth ligand. By withdrawing

1036

Figure 823.2 The tetrahedral Zn2+complexin carbonic anhydrase.

For Review and Reference

(Numbers in

parentheses

1037

refer to pages, unless noted otherwise.)

Learning Objectives
Relevant section and/or sample problem {SP}numbers
appear in parentheses.

Understand These Concepts

1. The positions of the d- and Fblock elements and the general
forms of their atomic and ionic electron configurations (Section
23.1)
2. How atomic size, ionization energy, and electronegativity vary
across a period and down a group of transition elements and how
these trends differ from those of the main-group clements; why
the densities of Period 6 transition clements are SO high (Section
23.1)
3. Why the transition elements often have multiple oxidation
states and why the + 2 state is common (Section 23.1)
4. Why metallic behavior (prevalence of ionic bonding and basic
oxides) decreases as oxidation state increases (Section 23.1)
5. Why many transition metal compounds are colored and para
magnetic (Section 23.1)
6. The common +3 oxidation state of lanthanides and the simi
larity in their M3 ~ radii; the radioactivity of actinides (Section
23.2)
7. How valence-state elecrronegativity explains why oxides be
come more covalent and acidic as the O.N. of the metal increases
(Section 23.3)
8. Why Cr and Mn oxoanions are stronger oxidizing agents in
acidic than in basic solutions (Section 23.3)
9. The role silver halides play in black-and-white photography
(Section 23.3)
10. How the high density and low melting point of mercury ac
count for its common uses; the toxicity of organomercury com
pounds (Section 23.3)
I L The coordination numbers, geometries. and ligand structures
of complex ions (Section 23.4)
12. How coordination compounds are named and their formulas
written (Section 23.4)
13. How Werner correlated the properties and structures of coor
dination compounds (Section 23.4)

14. The types of constitutional isomerism (coordination and link

age) and stereoisomerism (geometric and optical) of coordination
compounds (Section 23.4)
15. How valence bond theory uses hybridization to account for
the shapes of octahedral. square planar. and tetrahedral complexes
(Section 23.5)
16. How crystal field theory explains Ihat approaching ligands
cause d-orbital energies 10 split (Section 23.5)
17. How the relative crystal-field strength of ligands (spectro
chemical series) affects the d-orbital splitting energy (t.) (Section
23.5)
18. How the magnitude of t. accounts for the energy of light ab
sorbed and, thus, the color of a complex (Section 23.5)
19. How the relative sizes of pairing energy and Do determine the
occupancy of d orbitals and. thus, the magnetic properties of com
plexes (Section 23.5)
20. How d-orbital splitting in tetrahedral and square planar com
plexes differs from that in octahedral complexes (Section 23.5)

Master These Skills

I. Writing electron configurations of transition metal atoms and
ions (SP23.1)
2. Using a partial orbital diagram to determine the number of un
paired electrons in a transition-metal atom or ion (SP 23.2)
3. Recognizing the structural components of complex ions (Sec
tion 23.4)
4. Naming and writing formulas of coordination compounds (SP
23.3)
5. Determining the type of stereoisomerism in complexes (SP
23.4)
6. Correlating a complex ion's shape with the number and type of
hybrid orbitals of the central metal ion (Section 23.5)
7. Using the spectrochemical series to rank complex ions in terms
of Do and the energy of light absorbed (SP 23.5)
8. Using the spectrochemical series to determine if a complex is
high or low spin (SP 23.6)

Key Terms
transition elements (1003)
Section 23.1
lanthanide contraction (1006)
Section 23,2
lanthanides (IO to)
actinides (1010)
inner transition elements
(1010)

SeCtion 23.4
coordination compound
(1017)
complex ion (1017)
ligand (1017)
counter ion (1017)
coordination number (1018)
donor atom (1019)
chelate (1020)
isomer (l023)

constitutional (structural)
isomers (1023)
coordination isomers (1023)
linkage isomers (J024)
stereoisomers (1024)
geometric (cis-trans) isomers
(1024)
optical isomers (1024)
Section 23.5
coordinate covalent bond
(1026)

crystal field theory (1028)

e~orbital (1030\
t2.~orbital ( I030)
crystal field splitting energy
(t.) (030)

strong-field ligand (1030)

weak-field ligand (1030)
spectrochemical series (1031)
high-spin complex (1032)
low-spin complex (1032)

103

_ttttli

Chapter 21 The TransitionElements and Their Coordination

Compounds

Figures and Tables

These figures (F) and tables (T) provide a review of key

ideas. TIl.1 Orbital occupancy of Period 4 transition metals
(1005)
F2l.l Trends in atomic properties of Period 4 elements (1006)
F2l.4 Trends in key properties of the transition elements (1007)
T2l.2 Oxidation states and d-orbital occupancy of Period 4 transi
tion metals (l008)
T2l.6 Coordination numbers and shapes of complex ions (1019)
T2l.7 Common ligands in coordination compounds (1019)
T2l.8 Names of neutral and anionic ligands (1021)
T2l.9 Names of metal ions in complex anions (1021)

6. i f ~o uti

lIS to

IH[HItJ,IH[ i

23.5 Both metal ions are V3+; in terms of ligand field energy,
NH., > H20, so [V(NI'hl613+ absorbs light of higher energy.
23.6 The metal ion is Mn3+: [Ar] 3d4.

Follow-up Problems

23.1 (a) Ag +: 4d'o; (b) CdH: 4d'o; (c)

23.2 Three; EI;J+ is [Xel4fll:

OJ

t?+: 5d6

ill

1 ,--I

[i [

"""

'

6s
4/
5d
6p
23.3 (a) Pentaaquabromochromium(IIl) chloride;
(b) Ba3[Co(CN)6h
23.4 Two sets of cis-trans isomers, and the two cis isomers are op
tical isomers.

N...

trNa~ns],"
1
... Ct ~

(;l~Ct

r~

N..

]+

cNis~
I

geometric(;y~Ct

NH,

F21.10 Isomerism in coordination compounds (1023) F23.17d

Orbitals in an octahedral field of ligands (1029) F21.18 Splitting
of d-orbital energies by an octahedral field of li gands (1030)
F23.22 The spectrochemical series (1031)
F23.24 Orbital occupancy for high-spin and low-spin complexes
(1032)
F23.25 Splitting of d-orbital energies by a tetrahedral field of li
gands (1033)
F23.26 Splitting of d-orbital energies by a square planar field of
ligands (1034)

large

/j.

Two unpaired d electrons; low-spin complex

optical

NH3]+~ r:
t co'C"1,,t,,.....geometnc
Co

[N(NH.],J....1.,.:... CI
N I NH3
"'NH
CI
trans

N.......I.

Ct
cis

Problems with colored numbers are answered in Appendix E.

Sections match the text and provide the numbers of relevant
sample problems. Most offer Concept Review Questions,
Skill-Building Exercises (grouped in pairs covering the same
concept), and Problems in Context. Comprehensive Problems
are based on material from any section or previous chapter.
Note: In these problems, the term electron configuration
refers to the condensed, ground-state electron configuration.

Properties of the Transition Elements

(Sample Problem 23.1)

Concept Review Questions

23.1How is the 17 value of the d sublevel of a transition element re
lated to the period number of the element?
23.2 (a) Write the general electron configuration of a transition el
ement in Period 5.

(b) Write the general electron configuration of a transition ele

ment in Period 6.
23.3 What is the general rule concerning the order in which elec
trons are removed from a transition metal atom to form an ion?
Give an example from Group 5B(5). Name two types of mea
surements used to study electron configurations of ions.
21.4 What is the maximum number of unpaired d electrons that
an
atom or ion can possess'? Give an example of an atom and an
ion that have this number.
23.5 How does the variation in atomic size across a transition se
ries contrast with the change across the main-group elements of
the same period? Why?
21.6 (a) What is the lanthanide contraction?
(b) How does it affect atomic size down a group of transition el
ements?
(c) How does it influence the densities of the Period 6 transition
elements?

Problems
23.7 (a) What is the range in electronegativity values across the
first (3d) transition series?

(b) What is the range across Period 4 of main-group elements?

(c) Explain the difference between the two ranges.
23.8 (a) Explain the major difference between the number of oxi
dation states of most transition elements and that of most main
group elements.
(b) Why is the +2 oxidation state so common among transition
elements?
23.9 (a) What difference in behavior distinguishes a paramagnetic
substance from a diamagnetic one?
(b) Why are paramagnetic ions common among the transition
elements but not the main-group elements?
(C) Why are colored solutions of metal ions common among the
transition elements but not the main-group elements?

Skill-Building Exercises (grouped in similar pairs)

23.10 Using the periodic table to locate each element, write the
electron configuration of (a) V; (b) Y; (c) Hg.
23.11 Using the periodic table to locate each element, write the
electron configuration of (a) Ru; (b) Cu: (c) Ni.
23.12 Using the periodic table to locate each element, write the
electron configuration of (a) Os; (b) Co; (c) Ag.
23.13 Using the periodic table to locate each element, write the
electron configuration of (a) Zn: (b) Mn: (c) Re.
23.14 Give the electron configuration and the number of
unpaired electrons for each of the following ions: (a) Sc3+:
(b) Cu2"; (c) Fe3+; (d) Nb3+
23.15Give the electron configuration and the number or unpaired
electrons for each of the following ions: (a) C~"-; (b) 1j4+;
(c) Co~+; (d) Ta2+.
23.16 What is the highest possible oxidation state for each of the
following: (a) Ta; (b) Zr; (c) Mn?
23.17 What is the highest possible oxidation state Foreach of
the following: (a) Nb: (b) Y: (c) Tc?
23.18 Which transition metals have a maximum oxidation state of
+6?
23.19 Which transition metals have a maximum oxidation state of
+4?
23.20 In which compound does Cr exhibit greater metallic behav
ior, CrF2 or CrF~? Explain.
23.21 VFs is a liquid that boils at 48C, whereas VF3 is a solid
that melts above ROOCE. xplain this difference in properties,
23.22 Is it more difficult to oxidize Cr or Mo? Explain.
23.23 Is Mn04 - or Re04 - a stronger oxidizing agent? Explain.
23.24 Which oxide, Cr03 or CrO, forms a more acidic aqueous solution? Explain.
23.25 Which oxide, Mnz0-, or Mn20-I, displays more basic behav
ior? Explain.
Problems in Context
23.26 The green patina of copper-alloy roofs of old buildings is
the result of the corrosion (oxidation) of copper in the presence
of 020 H20, CO2, and sulfur compounds, Silver and gold-the
other stable members of Group IB( II )-do not form this patina.
Corrosion of copper and silver in the presence of sulfur and its
compounds leads to the familiar black tarnish. but gold does not
react with sulfur. This pattern is markedly different from that in

1039

Group IA( I), where ease of oxidation increases down the group.
What causes the different patterns in the two groups?

The Inner Transition Elements

(Sample Problem 23.2)

Concept Review Questions

23.27 What atomic property of the lanthanides leads to their re
markably similar chemical properties?
23.28 (a) What is the maximum number of unpaired electrons ex
hibited by an ion of a lanthanide?
(b) How does this number relate to occupancy of the 4fsubshell?
23.29 Which of the actinides are radioactive?
Skill-Building Exercises (grouped in similar pairs)
23.30 Write the electron configurations of the following atoms
and ions: (a) La; (b) Ce3+; (c) Es; (d) U4+.
23.31 Write the electron configurations of the following atoms
and ions: tal Pm; (b) Lu3+; (c) Th: (d) Fm3+.
23.32 Only a few of the lanthanides show any oxidation state
other than +3. Two of these, europium (Eu) and terbium (Tb),
are found near the middle of the series, and their unusual
oxidation states can be associated with a half-filledfsubshell.
(a) Write the electron configurations of Eu2+, Eu3+. and Eu4+.
Why is Eu2" a common ion, whereas Eu4+ is unknown?
(b) Write the electron configurations of Tb2+, Tb3+, and
Tb4-". Would you expect Tb to show a +2 or a +4 oxidation
state? Explain.
23.33 Cerium (Ce) and ytterbium (Yb) exhibit other oxidation
states in addition to +3.
(a) Write the electron configurations of Ce2+, Ce3 ". and Ce4+.
(b) Write the electron configurations of Yb2+, Yb3+, and YbH.
(c) In addition to the 3+ ions, the ions Ce4+ and Yb2+ are sta
ble. Suggest a reason for this stability.
Problems in Context
23.34 One of the lanthanides displays the maximum possible
number of unpaired electrons both for an atom and for a 3 + ion.
Name the element and give the number of unpaired electrons in
the atom and the ion.

Highlights of Selected Transition Metals

Concept Review Questions
23.35 What is the chemical reason that chromium is so useful for
decorative plating on metals?
23.36 What is valence-state electronegativity? Use the concept to
explain the change in acidity of the oxides of Mn with changing
O.N. of the metal.
23.37 What property does manganese confer to steel?
23.38 What chemical property of silver leads to its use in jewelry
and other decorative objects?
23.39 How is a photographic latent image different From the im
age you see on a piece of developed film?
23.40 Mercury has an unusual physical property and an unusual
I + ion. Explain.
Problems in Context
23.41 When a basic solution of Cr(OH)4- ion is slowly acidified,
solid Cr(OHh first precipitates out and then redissolves as
excess acid is added. Assuming that Cr(OH)4- actually exists
as Cr(H20h(0H)4 -, write equations that represent these two
reactions.

Chapter

104

23 The Transition Elements andProblems

Their Coordination Compounds

21.42 Use the following data to determine if Cf1+(aq) can be pre

pared by the reaction of Crts) with O"'+(aq):
C~+(aq)

+ e" ----- Cr~+({/q)

3e- CrH(aq) + 2e- C~+(aq)

Cnx)
Cr(s)

E'

-0.41 V

!! = -0.74 V
!! = -0.91 V

23.43 When solid Cr03 is dissolved in water, the solution is or

ange rather than the yellow of H:!Cr04. How does this observa
tion indicate that cr03 is an acidic oxide?
23.44 Solutions of KMn04 ale used commonly in redox titrations.
The dark purple Mn04 - ion serves as its own indicator, chang
ing to the almost colorless MnH as it is reduced. The end
point occurs when a pale purple color remains as the
KMn04 solution is added. If a sample that has reached this end
poinr is allowed to stand for a long period of time. the color
fades and a suspension of a small amount of brown, muddy
Mn02 appears. Use standard electrode potentials to explain this
result.

Coordination Compounds

(Sample Problems 23.3 and 23.4)

Concept Review Questions

23.45 Describe the makeup of a complex ion, including the nature
of the ligands and their interaction with the central metal ion.
Explain how a complex ion can be positive or negative and how
it occurs as part of a neutral coordination compound.
21.46 What electronic feature must a donor atom of any ligand
possess?
23.47 What is the coordination number of a metal ion in a complex
ion? How does it differ from oxidation number?
21.48 What structural feature is characteristic of a complex de
scribed as a chelate?
23.49 What geometries are associated with the coordination num
bers 2, 4, and 6?
23.50 What are the coordination numbers of cobalt(TII), plat
inum(Il), and plarinumttv)in complexes?
23.51 In what sense is a complex ion the adduct of a Lewis acid
base reaction?
23.52 What does the ending -ate signify in a complex ion name?
23.53 In what order are the metal ion and ligands given in the
name of a complex ion?
23.54 Is a linkage isomer a type of constitutional isomer or
stereoisomer? Explain.
Skill-Building Exercises (grouped in similar pairs)
23.55 Give systematic names for the following formulas:
(a) [Ni(H20)6)CI2
(b) [Cr(enh](CI04h
(c) ~[Mll(CN)61
23.56 Give systematic names for the following formulas:
(a) [ColNH3MN02hJCI
(b) [Cr(NH3)6][Cr(CN)6]
(c) K2[CuC141
23.57 What are the charge and coordination number of the central
metal ionts) in each compound of Problem 23.55?
23.58 What are the charge and coordination number of the central
metal ion(s) in each compound of Problem 23.56?
23.59 Give systematic names for the following formulas:
(a) K[Ag(CNhl (b) Na2[CdCl.J (c) [Co(NH3).,(HzO)Br]Br2
23.60 Give systematic names for the following formulas:
(a) K[Pt(NI-!3)CI5]
(b) [Cu(en)(NH3hHCo(en)CI41
(c) [Pt(enhBr2J(CI04h
23.61 What are the charge and coordination number of the central
metal ion(s) in each compound of Problem 23.59?

104

23.62 What are the charge and coordination number of the central
metal ion(s) in each compound of Problem 23.6O?
23.63 Give formulas corresponding to the following names:
(a) Terraamminezinc sulfate
(b) Pentaamminechlorochromium(IIl) chloride
(c) Sodium bis(thiosulfato)argentate(I)
23.64 Give formulas corresponding to the following names:
(a) Dibromobislethylenediamine)cobaltlIII) sulfate
(b) Hexaamminechromium(III) tetrachlorocuprate(lI)
(c) Potassium hexacyanoferraterll)
23.65 What is the coordination number of the metal
number of individual ions per formula unit in each
pounds in Problem 23.63?
23.66 What is the coordination number of the metal
number of individual ions per formula unit in each
pounds in Problem 23.64?

ion and the

of the com
ion and the
of the com

23.67 Give formulas corresponding to the following names:

(a) Hexaaquachromiumtlfl) sulfate
(b) Barium tetrabrornoterrarerlll)
(c) Bistethylenediarninejplatinumtll) carbonate
23.68 Give formulas corresponding to the following names:
(a) Potassium tris(oxalato)chromate(III)
(b) Tris(ethylenediamine)cobalt(lI [) pentacyanoiodomanganate( Il)
(c) Diamminediaquabromochloroaluminum nitrate
23.69 What is the coordination number of the metal
number of individual ions per formula unit ill each
pounds in Problem 23.67?
23.70 What is the coordination number of the metal
number of individual ions per formula unit in each
pounds in Problem 23.68?

ion and the

of the com
ion and the
of the com

23.71 Which of these ligands can participate in linkage isomerism:

(a) N02 ": (b) S02; (c) NOJ -? Explain with Lewis structures.
23.72 Which of these ligands can participate in linkage isomerism:
(a) SCN-; (b) S20/(rhiosulfare); (c) HS-? Explain with
Lewis structures.
23.73 For any of the following that can exist as isomers, state the
type of isomerism and draw the structures:
(a) [Pt(CH3NH2hBr2]
(b) [pt(NH3hFCl]
(c) lPt(H20)(NH])FCI]
23.74 For any of the following that can exist as isomers, state the
type of isomerism and draw the structures:
(a) [Zn(en)F21
(b) [Zn(H20)(NI-!3)FCI]
(c) [Pd(CN)z(OHhf23.75 For any of the following that can exist as isomers, state the
type of isomerism and draw the structures:
(a) [PtCI2Br2f(b) [Cr(NH3h(N02)f+
(c) Il't(NH3)4Izf+
23.76 For any of the following that can exist as isomers. state the
type of isomerism and draw the structures:
(a) [Co(NH3)sCI]Br2
(b) [P1(CI-!3NH2hCIlBr
(c) [Fe(H20MNH3h]2+
Problems in Context
23.77 Chromium(III), like cobalu lll), has a coordination number
of 6 in many of its complex ions. Compounds are known that
have the traditional formula CrCI3'nNH3, where 11 = 3 to 6.
Which of the compounds has an electrical conductivity in aque
ous solution similar to that of an equimolar NaCI solution?

23.78 When MCl~(NH3h is dissolved in water and treated with

AgN03, 2 mol of AgCl precipitates immediately for each mole

of MCI4(NH3}2. Give the coordination number of M in the
complex.
23.79 Palladium, like its group neighbor platinum, forms four
coordinate Pd(IJ) and six-coordinate Pd(!V) complexes. Write
modem formulas for the complexes with these compositions:
(a) PdK(NH})Ci]
(b) PdCl~(NH3h
(c) PdK2Ci6
(d) Pd(NH3)4Cl4

Theoretical Basis for the Bonding and Properties

of Complexes
(Sample Problems 23.5 and 23.6)
Concept Review Questions
23.80 tal What is a coordinate covalent bond?
(b) Is it involved when FeCI] dissolves in water? Explain.
(c) Is it involved when HCI gas dissolves in water? Explain.
23.81 According to valence bond theory, what set of orbitals is
used by a Period 4 metal ion ill forming (a) a square planar
complex; (b) a tetrahedral complex?
23.82 A metal ion is described as using a d2spJ set of orbitals
when forming a complex. What is the coordination number of
the metal ion and the shape of the complex?
23.83 A complex in solution absorbs green light. What is the color
of the solution?
23.84 What MO possibilities of color absorption by a solution
could give rise to an observed blue color?
23.85 (a) What is the crystal field splitting energy (A)?
(b) How does it arise for an octahedral field of ligands?
(c) How is it different for a tetrahedral field of ligands?
23.86 What is the distinction between a weak-field ligand and a
strong-field ligand? Give an example of each.
23.87 Is a complex with the same number of unpaired electrons as
the free gaseous metal ion termed high spin or low spin?
23.88 How do the relative magnitudes of Epa;.;ng and ~ affect the
paramagnetism of a complex?
23.89 Why are there both high-spin and low-spin octahedral com
plexes but only high-spin tetrahedral complexes?
Skill-Building Exercises (grouped in similar pairs)
23.90 Give the number of d electrons (n of d'') for the central
metal
ion6]3-.
in each of these species: (a) [TiCI6f-: (b) K[AuCI4J;
(c) [RhCl
23.91 Give the number of d electrons (/1 of d") for the cen
tral metal ion in each of these species: (a) [Cr(H20)61(CI03b
(b) [Mn(CN}6f-; (c) [Ru(NO)(enhCI]Br.
23.92 Give the number of d electrons (/1 of d'") for the cen
tral metal ion in each of these species: (a) Ca[lrF61;
(b) rHgI4f-: (c) [Co(EDTA)f-.
23.93 Give the number of d electrons (11 of dn) for the cen
tral metal ion in each of these species: (a) [Ru(NH3)5CI1S04;
(b) Na2[Os(CN)bl; (c) [Co(NHJJ4COJI].
23.94 Sketch the orientation of the orbitals relative to the ligands
in an octahedral complex to explain the splitting and the relative
energies of the d,., and the d."'_,.2 orbitals.
23.95 The two e~ orbitals are identical in energy in an octahedral
complex but have different energies in a square planar complex,
with the do, orbital being much lower in energy than the d"'_y2.
Explain with orbital sketches.
23.96 Which of these ions cannot form both high- and low-spin
octahedral complexes: (a) Ti3+; (b) C02+; (c) Fe2+; (d) Cu1+?

23.97 Which of these ions cannot form both high- and low-sfin
octahedral complexes: (a) Mn3+; (b) Nb3+; (c) Ru3+; (d) Ni-+?
23.98 Draw orbital-energy splitting diagrams and use the spectro
chemical series to show the orbital occupancy for each of the fol
lowing (assuming that H20 is a weak-field ligand):
(a) [Cr(H20)6]3+
(b) (Cu(H20)4f+
Cc){FeF6]323.99 Draw orbital-energy splitting diagrams and use the spectro
chemical series to show the orbital occupancy for each of the
fol lowing (assuming that H20 is a weak-field ligand):
(a) [Cr(CN)6]3(b) [Rh(CO)6]3+
(c) [CO(OH)6]423.100 Draw orbital-energy splitting diagrams and use the spec
trochemical series to show the orbital occupancy for each of the
following (assuming that H20 is a weak-field ligand):
(a) [MoCI6]3(b) [Ni(H20)6f+
(c) [Ni(CN)4]223.101Draw orbital-energy splitting diagrams and use the spectro
chemical series to show the orbital occupancy for each of the fol
lowing (assuming that H20 is a weak-field ligand):
(a) [Fe(C204hP- (C20l- creates a weaker field than H20 does.)
(b) [CO(CN)6ttc) [MnCI61423.102 Rank the following complex ions in order of increasing ~
and energy of visible light absorbed: [Cr(NH3)613+,
[Cr(H20)6]3+, [Cr(N02)613- .
23.103 Rank the following complex ions in order of decreasing ~
and energy of visible light absorbed: [Cr(enh]3+. [Cr(CN)6]3- .
[CrCI,;13-.
23.104 A complex. ML62+. is violet. The same metal forms a
com plex with another ligand. Q, that creates a weaker field.
What color might MQ62+ be expected to show? Explain.
23.105 [Cr(H20)6f+ is violet. Another Crl.; complex is green.
Can ligand L be CN-? Can it be Cl"? Explain.
Problems in Context
23.106 Octahedral [Ni(NH3)6f+ is paramagnetic. whereas planar
[Pt(NH3)4f+ is diamagnetic, even though both metal ions are dS
species. Explain.
23.107 The hexaaqua complex [Ni(H20)6f+ is green, whereas
the
hexaamrnonia complex [Ni(NHJ)J2+ is violet. Explain.
23.108 Three of the complex ions that are formed by CoH
are rCo(H20)613+. [Co(NH])613+, and [CoF6J3-. These ions
have the observed colors (listed in arbitrary order) yelloworange,
green, and blue. Match each complex with its color. Explain.

Comprehensive Problems
23.109 When neptunium (NpJ and plutonium (Pu) were discov
ered, the periodic table did not include the actinides, so these el
ements were placed in Group 7B(7) and SE(S). When americium
(Am) and curium (Cm) were synthesized. they were placed in
Group SB(9) and 8B( to). However, during chemical isolation
procedures, Glenn Seaborg and his group, who had synthesized
these elements, could not find their compounds among other
compounds of these groups, which led Seaborg to suggest they
were part of a new inner transition series. (a) How do the elec
tron configurations of these elements support Seaborg's sugges
tion? (b) The highest fluorides of Np and Pu are hexafluorides, as
is the highest fluoride of uranium. How does this chemical evi
dence support the placement of Np and Pu as inner transition el
ements rather than transition elements?
23.110How many different formulas are there for octahedral com
plexes with a metal M and four ligands A, B, C and D? Give the
number of isomers for each formula and describe the isomers.

Chapter 23 The Transition Elements andProblems

Their Coordination Compounds

1041

23.111At one time. it was common to write the formula for cop
per(l) chloride as CuzClz, instead of CuCl. analogously to
HgzClz for mercury(1) chloride. Use electron configurations to
explain why Hg2CI2 is correct but so is CuC).
23.112Correct each name that has an error: (a)
Na(FeBr41, sodium tetrabromoferrate(lI) (b)
[Ni(NH3)6f+. nickel hexaamminc ion (c)
[Co(NH3hI3J, triamminetriiodocobalt(lll)
(d) [V(CN)613-, hexacyanovanadiumtfll) ion
(e) K[FeCI4J. potassium tetrachloroiron(II1)
23.113For the compound [Co(enhCl2JCI, give:
(a) The coordination number of the metal ion
(b) The oxidation number of the central metal ion
(c) The number of individual ions per formula unit
(d) The moles of AgCl that precipitate immediately when I mol
of compound is dissolved in water and treated with AgNO~
23.114Hexatluorocobaltatet llf) ion is a high-spin complex. Draw
the orbital-energy splitting diagram for its d orbitals.
23.115A salt of each of the ions in Table 23.3 (p. 1009) is
dissolved
in water. A Pt electrode is immersed in each solution and con
nected to a 0.38- V battery, All of the electrolytic cells are run
for the same amount of time with the same current.
(a) In which cell(s) will a metal plate out? Explain.
(b) Which cell will plate out the least mass of metal? Explain.
23.116 Criticize and correct the following statement: strong-field
ligands always give rise to low-spin complexes.
23.117 Two major bidentate ligands used in analytical
chemistry are bipyridyl (bipy) and ortho-phenanthroline (ophen):

bipyridyt

o-phenanthroline

Draw structures and discuss the possibility of isomers for

(a) [Pt(bipy)CI2J
(b) [Fe(o-phenhlH
(c) [Co(bipyhFzJ+
(d) rCo(o-phen)(NH3hCI12+
23.118 The following reaction is a key step in black-and-white
photography (see p. 1015):
AgBr(s) + 2S20/-(aq) ---+ Ag(SZ03h3-(aq) + Br-(aq)
During fixing, 258 mL of hypo (sodium thiosulfate) was used.
The hypo concentration was 0.1052 M before the AgBr reacted,
and 0.0378 M afterward. How many grams of AgBr reacted?
23.119 The metal ion in platinum(TV) complexes. like that in
cobalt(III) complexes. has a coordination number of 6. Many of
these complexes occur with CI- ions and NH3 molecules as li
gands. Consider the following traditional (before the work of
Werner) formulas for two coordination compounds:
(a) PtCI.6NHj
(b) PtCl.j4NHj
For each of these compounds:
(l) Give the modem formula and charge of the complex ion.
(2) Predict moles of ions formed per mole of compound
dissolved and moles of AgCl formed immediately with excess
AgNOJ.
23.120 In 1940, when the elements Np and Pu were prepared. a
controversy arose about whether the elements from Ac on were
analogs of the transition elements (and related to Y through Mo)
or analogs of the lanthanides (and related to La through Nd). The
arguments hinged primarily on comparing observed oxidation
states to those of the earlier elements. (a) If the actinides were

analogs of the transition elements. what would you predict about

the maximum oxidation state for U? For Np? (b) If the actinides
were analogs of the lanthanides, what would you predict about
the maximum oxidation state for U? For Pu?
23.121In many species. a transition metal has an unusually high or
low oxidation state. Write balanced equations for the following
and tind the oxidation state of the transition metal in the product:
(a) Iron(III) ion reacts with hypochlorite ion in basic solution to
form ferrate ion (FeO/-), CI-, and water.
(b) Potassium hexacyanomanganaterll) reacts with K metal to
form K6(Mn(CN)6]'
(c) Heating sodium superoxide with C0304 produces N3.JC004
and O2 gas.
(d) Vanadium(TII)chloride reacts with Na metal under a CO at
mosphere to produce Na[V(CO)61 and NaCI.
(e) Barium peroxide reacts with nickel(ll) ions in basic solution
to produce BaNiO,.
(f) Bubbling CO through a basic solution of cohalt(II) ion pro
duces [CO(CO)4r, C032-, and water.
(g) Heating cesium tetraftuorocuprate(JT) with F2 gas under
pres
sure gives C~CUF6'
(h) Heating tantalumt V) chloride with Na metal produces NaCI
and Ta6C115,in which half of the Ta is in the +2
state.
(i) Heating cesium tetrafluoroargentate(Il) with F2 gas gives
Cs2AgF6' in which half the silver is in the +3 state.
U) Potassium tetracyanonickelate(1I) reacts with hydrazine
(NzH4) in basic solution to form K.[Ni2(CN)61 and N2
gas.
23.122 For the permanganate ion, draw a Lewis structure that has
the lowest formal charges.
23.123 The coordination compound [Pt(NH]h(SCNhl displays
two types of isomerism. Name the types and give names and
structures for the six possible isomers.
23.124 In the sepia "toning" of a black-and-white photograph, the
image is converted to a rich brownish violet by placing the fin
ished photograph in a solution of goldtfll) ions. in which metal
lic gold replaces the metallic silver. Use Appendix D to explain
the chemistry of this process.
23.125 An octahedral complex with three different ligands (A. B.
and C) can have formulas with three different ratios of the
ligands: [MA4BCl"+,
such as [Co(NH~MH20)Clf+
[MA3B2C]"+, such as [Cr(H20hBr2CI]
[MAzBzCzJ"+, such as [Cr(NH]h(HzOhBrzl+
For each example, give the name, state the type(s) of isomerism
present. and draw all isomers.
23.126 In black-and-white photography, what are the major chem
ical changes involved in exposing, developing, and fixing?
23.127 In [Cr(NH3)6]CI3, the [CrtNH])6]3+ ion absorbs visible
light in the blue-violet. range. and the compound is yellow
orange. In [Cr(H20)6JBr3' the [Cr(H20)6f+ ion absorbs visible
light in the red range. and the compound is blue-gray. Explain
these differences in light absorbed and colors of the compounds.
23.128 Dark green rnanganate salts contain the MnOl- ion. The
ion is stable in basic solution but disproportionates in acid to
Mn02(S) and Mn04 -. (a) What is the oxidation state of Mn in
Mn042-, Mn04 -. and Mn02? (b) Write a balanced equation for
the reaction of Mn042- in acidic solution.
23.129 Aqueous electrolysis of potassium manganate (KzMn04)
in basic solution is used for the production of tens of thousands
of tons of potassium permanganate (KMnO.) annually. (a) Write

104

a balanced equation for the electrolysis reaction. (Water is re

duced also.) (b) How many moles of Mn04 - can be formed if
12 A flow through a tank of aqueous Mn042- for 96 h?

23.130 The actinides Pa. U, and Np form a series of complex ions.

such as the anion in the compound Na3[UFH],in which the cen
tral metal ion has an unusual geometry and oxidation state. In the
crystal structure, the complex ion can be pictured as resulting
from interpenetration of simple cubic arrays of uranium and fluo
ride ions. (a) What is the coordination number of the metal ion in
the complex ion? (b) What is the oxidation state of uranium in
the compound? (c) Sketch the complex ion.
23.131 Ionic liquids have many new applications in engineering
and materials science. The dissolution of the rnetavanadate ion
in chloroaluminate ionic liquids has been studied:
V03 - + AICI4- -V02CI2 - + AIOC12(a) What is the oxidation number of V and AI in each ion'!
(b) In reactions with V205' acid concentration affects the prod
uct. At low acid concentration, V02CI2 - and V03 form: V20S + HCI -V02Cl2- + V03- +
H+
At high acid concentration. VOCI3 forms:
V20~ + HCI-VOC13 + H20
Balance each equation, and state which. if either. involves a re
dox process.
(c) What mass of V02CI2 - or VOC1) can form from 10.0 g of
V20S and the appropriate concentration of acid?
23.132 (a) What are the central metal ions in chlorophyll, heme.
and vitamin BI2? (b) What similarity in structure do these com
pounds have?
23.133 Several coordination isomers, with both Co and Cr as 3+
ions, have the molecular formula CoCrC6HISN12' (a) Give the
name and standard formula of the isomer in which the Co com
plex ion has six NH3 groups. (b) Give the name and standard for
mula of the isomer in which the Co complex ion has one CN and
five NH3 groups,
23.134 There are several coordination isomers with the molecular
formula PI2HI2C16N4'(a) Give the name and standard formula
of the isomer in which the Pt complex ion has six CI groups and
a charge of 2 -. (b) Give the name and standard formula of the
isomer in which the Pt complex ion has four CI groups and a
charge of 2 - .
23.135 A shortcut to finding optical isomers is to see if the complex
has a "plane of symmetry"-a plane passing through the metal
atom such that every atom on one side of the plane is matched by
an identical one at the same distance from the plane on the other
side, Any planar complex has a plane of symmetry, since all
atoms lie in one plane. Use this approach to determine whether
these exist as optical isomers: (a) [Zn(NH~)zCI21(tetrahedral);
(b) [Pt(en)zf+; (c) rl"afls-[PtBr4C12f-; (d) trans-[Co(en)2F2]+;
(e) cis-[Co(enhF2]+.
23.136 Werner prepared two compounds by heating a solution of
PtClz with triethyl phosphine. P(C2H5h, which is an excellent
ligand for Pt. The two compounds gave the same analysis: Pt.
38.8%; CI, 14.1%; C, 28.7%; P. 12.4%; and H, 6.02%. Write
formulas, structures, and systematic names for the two isomers.
23.137 Some octahedral complexes have distorted shapes, In the
Jahn-Teller distortion, two metal-ligand bonds that are 1800

apart are shorter than the other four. In [Cu(NH3)6f+, for exam
ple, two Cu-N bonds are 207 pm long, and the other four are
262 pm Long. (a) Calculate the longest distance between two
N atoms in this complex. (b) Calculate the shortest distance
be tween two N atoms.
23.138 Mercury has a small but significant vapor pressure, and Hg
poisoning can occur in poorly ventilated rooms where Hg has
been spilled, What is the partial pressure of Hg at 25C for a
maximum concentration of 20.0 mg/rrr'?
23.139 Normal carbonic anhydrase has zinc at its active site (see
Figure B23,2, p. 1036). Suggest a structural reason why carbonic
anhydrase synthesized with NiH. Fe2+, or Mn2+ in place of
Zn2+ gives an enzyme with less catalytic efficiency.
23.140 The effect of entropy on reactions is evident in the stabili
ties of certain complexes.
(a) Using the criterion of number of product particles. predict
which of the following will be favored in terms of u.s?xn:
[Cu(NH3)4f+(aq) + 4H20(l)[Cu(H20)4l"+(aq) + 4NH3({/q)
[Cu(H2NCH2CH2NH2h]2+(aq)

+ 4H20(l)

[Cu(H20)4f+(aq) + 2en({/q)
(b) Given that the Cu-N bond strength is approximately the
same in both complexes, which complex will be more stable
with respect to ligand exchange in water? Explain.
23.141 The extent of crystal field splitting is often determined from
spectra.
(a) Given the wavelength (;>'_) of maximum absorption, find the
crystal field splitting energy (~), in kllmol, for each or the fol
lowing complex ions:
Ion
rCr(H2O)613+
[Cr(CN)6]3[CrCI6]3[Cr(NH3)613+
[Ir(NH3)6]H

>'(nm)
562
381
735
462
244

Ion
[Fe(H2O)6f+
[Fe(H10)()]3+
[Co(NH1)6JH
[Rh(NH3)6]3+

;>,_(nm)
966
730
405
295

(b) Construct a spectrochemical series for the ligands in the Cr

complexes.
(c) Use the Fe data to state how oxidation state affects A.
(d) Use the Co. Rh, and Ir data to state how period number af
fects j,.
23.142 You know the following about a coordination compound:
(I) The partial empirical formula is KM(Cr0-l)CI2(NH3)4'
(2) It has A (red) and B (blue) crystal forms.
(3) When 1,0 mol of A or B reacts with 1.0 mol of AgN03,
0.50 mol of a red precipitate forms immediately.
(4) After the reaction in (3), 1.0 mol of A reacts very slowly
with
1.0 mol of silver oxalate (Ag2C204) to form 2.0 mol of a white
precipitate. (Oxalate can displace other ligands.)
(5) After the reaction in (3). 1.0 mol of B does not react further
with 1.0 mol of AgN03
From this information, determine the following:
(a) The coordination number of M
(b) The group(s) bonded to M ionicaJly and covalently
(c) The stereochemistry of the red and blue forms