CHEM1902 (C10K) Coordination Chemistry Tutorials

From the May 2004 Exam Paper.

1). (a) Give the Oxidation number, d-orbital occupation, co-ordination number and
expected magnetic moment of the central metal ion in the following complexes.
Draw the expected structure.
(i) K3[Co(C2O4)3]
(ii) (NH4)2[CoF4]
(iii) diamagnetic [NiCl2{P(C6H5)3}2]
(iv) cis-[CrCl2(bipy)2]Cl
(v) [Mn(H2O)6]SO4
where C2O42- is the oxalate ion and bipy is 2,2'-bipyridine.
(b) Which of the complexes above can exhibit isomerism? Explain.
(c) Give the IUPAC name for the complex (ii) in part (a).
Answers
2) Write down the systematic name for each of the following complexes and indicate
the coordination number, oxidation number, electronic configuration, stereochemistry
and magnetic moment of the central ion.
a. K[Cr(oxal)2(H2O)2].3H2O
b. CrCl3(py)3
c. K4[Mn(CN)6]
d. [CoCl(NH3)5]Cl2
e. Cs[FeCl4]
f. [NiCl(NH3)(en)2]Cl
g. [Cu(NH3)4(H2O)]SO4
Answers
3) The hexaquo manganese(II) ion contains five unpaired electrons, while the

hexacyano- ion contains only one unpaired electron. Explain, using Crystal Field
Theory.
Answers
4) Indicate the type of isomerism exhibited by the following complexes and draw
structures for these isomers.
a. K[Cr(oxal)2(H2O)2].3H2O
b. [Co(en)3]Cl3
c. [CoCl(NO2)(NH3)4]Br
d. PtCl2(NH3)(H2O)
Answers
5) Give an example of each of the following:
a. Binuclear Complex
b. Metal Chelate
c. Low spin complex
d. High spin complex
e. Five coordinate complex.
6) a) Place the following ligands in increasing order in the Spectrochemical series:
CN-, NH3, Cl-,H2O
b) For octahedral first row transition metal complexes with between four and seven d
electrons, both high and low spin electron configurations are possible.
Use Crystal Field splitting diagrams to determine the number of unpaired electrons
and then calculate the expected spin-only magnetic moments.
7) a) Draw the complex, [Ni(en)3]2+, showing the optical isomers.

b) If at equilibrium, [Ni(en)3]2+, is 0.08M and [en] is 0.40M, calculate [Ni 2+].

Note that 3 for [Ni(en)3]2+ is 4.07 x 1018.
c) Write equations for the successive formation equilibria.
d) The first and second stepwise formation constants are:
log K1 =
7.66
and
log K2 =
6.40.
Calculate the third stepwise formation constant.
Ans
b)
3.07 x 10-19.
d)
3.55 x 104.

8) The complex ion [Ni(NH3)4]2+, forms on mixing aqueous solutions of ammonia and
a nickel salt.
a) If a solution contains 1.6 x 10-4 % of the nickel ions in the form of Ni2+ when the
concentration of free NH3 (aq) is 0.5M. What is the stability constant of the complex
[Ni(NH3)4]2+?
(Assume that this is the only complex present).
b) The octahedral ammine complex can be prepared by using a solution of ammonia
which has been supersaturated with ammonia gas, such that:
log K5 = 0.85
log K6 = 0.42.
Calculate the overall 6 for [Ni(NH3)6]2+.
Write the equations for the equilibria corresponding to K5 and K6.
Coordination Chemistry - CHEM1902 (C10K)
Answers to Tutorial Paper - 1
From the May 2004 Exam Paper.
1). (a) Give the Oxidation Number, d-orbital occupation, co-ordination number and
expected magnetic moment of the central metal ion in the following complexes.
Draw the expected structure.
(i) K3[Co(C2O4)3]
This octahedral Co(III) complex can display optical isomerism.
The CN = 6, the OS=3+, the d-orbital occupation is that of a LOW spin Co(III)
complex ie t2g6 eg0. All Co(III) are treated as LOW spin for CHEM1902 (C10K).

The magnetic moment is therefore 0 B.M.

(ii) (NH4)2[CoF4]
This Co(II) complex is tetrahedral (for CHEM1902 (C10K) we have said that square
planar complexes will only be seen for d8 configurations and Co(II) is d7.
The d-orbital configuration is e4 t23 and the magnetic moment is 3.87 B.M { sqrt(15) }.
(iii) diamagnetic [NiCl2{P(C6H5)3}2]
The indication that the compound is diagmagnetic means it must be square planar
since a Ni(II) d8 configuration in a tetrahedral shape would be paramagnetic.
Examples with this formulation in BOTH tetrahedral and square planar shapes have
been found, generally the tetrahedral are green/blue while the square planar are red.
The triphenyl phosphine ligand is a neutral monodentate ligand.
(iv) cis-[CrCl2(bipy)2]Cl
Cr(III) has a d3 configuration (t2g3).
In this octahedral complex we do not need to worry about high/low spin since we
always fill from the lower level and there are 3 t 2g orbitals and 3 electrons and no
electrons left to occupy the eg level.
(v) [Mn(H2O)6]SO4
The aqua group gives rise to HIGH spin complexes so this octahedral Mn(II) d5
complex is paramagnetic with 5 unpaired electrons (t 2g3 eg2).
(b) Which of the complexes above can exhibit isomerism? Explain.
(i) can exhibit optical isomerism
(ii) does NOT show isomerism
(iii) the known square planar complexes with this formula are trans- and cis- forms
are theoretically possible.

(iv) The cis- form can exhibit optical isomerism and there is a possibility of
a trans- form as well.
(v) does NOT show isomerism.
(c) Give the IUPAC name for the complex (ii) in part (a).
ammonium tetrafluorocobaltate(II)
Note that the NH4+ cation is not coordinated and must be named before the anion.
2) Write down the systematic name for each of the following complexes and indicate
the oxidation state, electronic configuration, coordination number, stereochemistry
and magnetic moment of the central ion.
a) K[Cr(oxal)2(H2O)2] .3H2O
potassium diaquabis(oxalato)chromate(III) trihydrate
OS= 3, d3, t2g3eg0, CN=6, Shape =octahedral, 3 unpaired electrons.
b) CrCl3(pyr)3
trichloridotripyridinechromium(III)
OS= 3, d3, t2g3eg0, CN=6, Shape =octahedral, 3 unpaired electrons.
c) K4[Mn(CN)6]
potassium hexacyanidomanganate(II)
OS= 2, d5, t2g5eg0, CN=6, Shape =octahedral, 1 unpaired electron.
d) [CoCl(NH3)5] Cl2
pentaamminechloridocobalt(III) chloride
OS= 3, d6, t2g6eg0, CN=6, Shape =octahedral, 0 unpaired electrons. *
e) Cs[FeCl4]
caesium tetrachloridoferrate(III)
OS= 3, d5, e2t23, CN=4, Shape =tetrahedral**, 5 unpaired electrons.
f) [NiCl(en)2(NH3)]Cl
amminechlorobis(1,2-diaminoethane)nickel(II) chloride
OS= 2, d8, t2g6eg2, CN=6, Shape =octahedral, 2 unpaired electrons.
g) [Cu(NH3)4(H2O)]SO4
tetraammineaquacopper(II) sulfate
OS= 2, d9, splitting pattern not done for CHEM1902 , CN=5, Shape =square pyramid,
1 unpaired electron. (With 5 d-orbitals that can hold 10 electrons and Cu(II) with 9

electrons then it must mean there is 1 unpaired electron irrespective of the splitting
pattern of the energies of the d orbitals)
* for CHEM1902 (C10K), assume all Co(III) complexes are low-spin.
** for CHEM1902 (C10K), assume the only square planar complexes are for
d8 configurations
4) The hexaaquamanganese(II) ion contains five unpaired electrons, while the
hexacyano- ion contains only one unpaired electron. Explain, using Crystal Field
Theory.
Octahedral complexes with between 4 and 7 d electrons can give rise to either high or
low spin magnetic properties. Mn(II) has a d 5 configuration. In a weak octahedral
crystal field this splits to give t2g3eg2 but in a strong crystal field it gives t2g5eg0.
In the first case no pairing of electrons occurs, but in the second 2 pairs of electrons
are present leaving only one unpaired electron.
5) Indicate the type of isomerism exhibited by the following complexes and draw
structures for these isomers.
a) K [Cr(oxal)2(H2O)2] .3H2O
Both geometric (cis-, trans-) and optical isomers can exist.
b) [Co(en)3]Cl3
Two optical isomers can exist
c) [CoCl(NO2)(NH3)4]Br
Note that there are 10 possible isomers!
Hint: There are geometric, ionisation and linkage isomers possible.
d) PtCl2(NH3)(H2O)
Geometric (cis-, trans-) isomers can exist.
6)

Ans.

a)
b)

1.0 x 107.
1.9 x 108.

a) The total amount of Ni2+ in the solution is given by:

Total Ni2+ = Ni2+ + NiL2+ + NiL22+ + NiL32+ + NiL42+
If we assume that the only complex formed is NiL 42+ then this simplifies to:
Total Ni2+ = Ni2+ + NiL42+
If the solution contains 1.6 x 10-4 % of the Ni in the free form then this means that:
Ni
---------5.1)

100

1.6 x 10 ^-4

(equation

Ni + NiL4

But since the amount of free Ni2+ is extremely small then the Total Ni(II) can be
approximated to NiL42+

The stability constant for the reaction forming the tetraammine is:
K

NiL4
--------Ni L^4

(equation 5.2)

Given that the NH3 concentration is 0.5M then equilibrium expression (equation 5.2)
can be simplified once it is recognised that the relationship in equation 5.1 is the
reciprocal of part of equation 5.2.
In other words the stability constant (K or 4) is
K

100
---------------------[1.6 x 10^-4] [0.5]^4

or 4 = 1.0 x 107
b) log 6 = log 4 + Log K5 + Log K6
Having just calculated 4 and given the last two stepwise stability constants then the
overall stability constant is:
log 6 = 7.0 + 0.85 + 0.42 = 8.27
or 6 = 1.9 x 108
6)
b)
K

[Nien3]
---------[Ni] [en]^3

(equation 6.1)

If at equilibrium [Ni(en)3]2+ is 0.08M and [en] is 0.40M then given that 3 is 4.07 x
1018
the concentration of free Ni2+ can be expressed as:
Ni

[Nien3]
---------K [en]^3

or Ni2+ = 3.07 x 10-19

d) If 3 is 4.07 x 1018 then log 3 is 18.61
log 3 = log K1 + log K2 + log K3
Given that log K1 = 7.66 and log K2 = 6.40 then
log K3 = 18.61 - 7.66 - 6.40
or log K3 = 4.55 and K3 = 3.55 x 104

(equation 6.2)

Magnetic Moments
Lecture 4. CHEM1902 Coordination Chemistry
Magnetic moments are often used in conjunction with electronic spectra to gain
information about the oxidation number and stereochemistry of the central metal ion
in coordination complexes.
A common laboratory procedure for the determination of the magnetic moment for a
complex is the Gouy method which involves weighing a sample of the complex in the
presence and absence of a magnetic field and observing the difference in weight. A
template is provided for the calculations involved.
For first row transition metal ions in the free ion state, i.e. isolated ions in a vacuum,
all 5 of the 3d orbitals are degenerate.
A simple crystal field theory approach to the bonding in these ions assumes that when
they form octahedral complexes, the energy of the d orbitals are no longer degenerate
but are split such that two orbitals, the dx2-y2 and the dz2 (eg subset) are at higher energy
than the dxy, dxz, dyz orbitals (the t2g subset).
For octahedral ions with between 4 and 7 d electrons, this gives rise to 2 possible
arrangements called either high spin/weak field or low spin/strong field respectively.
The energy gap is dependent on the position of the coordinated ligands in the
SPECTROCHEMICAL SERIES.
See an interactive JAVA applet for examples.
Note: For CHEM1902 (C10K), we assume that all Co(III), d6 complexes are
octahedral and LOW spin, i.e. t2g6.
In tetrahedral complexes, the energy levels of the orbitals are again split, such that the
energy of two orbitals, the dx2-y2 and the dz2 (e subset) are now at lower energy (more
favoured) than the remaining three dxy, dxz, dyz (the t2 subset) which are destabilised.
Tetrahedral complexes are ALL high spin since the difference between the 2
subsets of energies of the orbitals is much smaller than is found in octahedral
complexes.
The usual relationship quoted between them is: tet 4/9 oct.

Square planar complexes are less commmon than tetrahedral and for CHEM1902 we
will assume that the only ions forming square planar complexes are d8 e.g. Ni(II),
Pd(II), Pt(II), etc. As with octahedral complexes, the energy gap between the dxy and
dx2-y2 is oct and these are considered strong field / low spin hence they are all
diamagnetic, =0 Bohr Magneton (B.M.)
The formula used to calculate the spin-only magnetic moment can be written in two
forms; the first based on the number of unpaired electrons, n, and the second based on
the electron spin quantum number, S. Since for each unpaired electron, n=1 and S=1/2
then the two formulae are clearly related and the answer obtained must be identical.
so= n(n+2) B.M.
so= 4S(S+1) B.M.
Comparison of calculated spin-only magnetic moments
with experimental data for some octahedral complexes
Ion

Config
1

so / B.M. obs / B.M.

Ti(III)

d (t2g )

3 = 1.73 1.6-1.7

V(III)

d2 (t2g2)

8 = 2.83 2.7-2.9

Cr(III)

d (t2g )

15 = 3.88 3.7-3.9

Cr(II)

d4 high spin (t2g3 eg1) 24 = 4.90 4.7-4.9

Cr(II)

d4 low spin (t2g4)

8 = 2.83 3.2-3.3

Mn(II)/ Fe(III) d5 high spin (t2g3 eg2) 35 = 5.92 5.6-6.1

Mn(II)/ Fe(III) d5 low spin (t2g5)
6

3 = 1.73 1.8-2.1
2

Fe(II)

d high spin (t2g eg ) 24 = 4.90 5.1-5.7

Co(III)

d6 low spin (t2g6)

7

Co(II)

d high spin (t2g eg ) 15 = 3.88 4.3-5.2

Co(II)

d7 low spin (t2g6 eg1)

8

3 = 1.73 1.8

Ni(II)

d (t2g eg )

8 = 2.83 2.9-3.3

Cu(II)

d9 (t2g6 eg3)

3 = 1.73 1.7-2.2

Comparison of calculated spin-only magnetic moments

with experimental data for some tetahedral complexes
Ion
Cr(V)

Config
d1 (e1)

so / B.M.
3 = 1.73

obs / B.M.
1.7-1.8

Cr(IV) / Mn(V)

d2 (e2)

Fe(V)

d3 (e2 t21)
4

8 = 2.83

2.6 - 2.8

15 = 3.88

3.6-3.7

d (e t2 )

24 = 4.90

Mn(II)

d5 (e2 t23)

Fe(II)

35 = 5.92

5.9-6.2

24 = 4.90

5.3-5.5

d (e t2 )

Co(II)

d (e t2 )

15 = 3.88

4.2-4.8

Ni(II)

d8 (e4 t24)

8 = 2.83

3.7-4.0

3 = 1.73

Cu(II)

d (e t2 )

Problem Set 10
1. Werner also studied the electrical conductance of aqueous solutions containing a
series of platinum(IV) complexes having the general formula Pt(NH 3)xCl4, where x is
an integer that varied from 2 to 6. His results can be summarized as:
Formula of Complex

Number of ions produced upon complete

dissociation

Pt(NH3)6Cl4

Pt(NH3)5Cl4

Pt(NH3)4Cl4

Pt(NH3)3Cl4

Pt(NH3)2Cl4

Assuming that Pt(IV) forms octahedral complexes, (a) write the formulas for the five
compounds based on the dissociation results, (b) draw three-dimensional sketches of
the complexes, (include isomers that are possible), and (c) name each compound.

2. Crystal Field Theory fails in explaining why a neutral ligand such as CO can cause
a very large crystal field splitting. Use Molecular Orbital Theory to explain why the
CO ligand leads to a higher crystal field splitting.

3. In a linear field (as experienced, for example, by the d electrons in [Ag(NH 3)2]+),
how would Crystal Field Theory arrange the d orbitals according to increasing energy.
(Hint: Take z as the unique axis)

4. When Pt has a coordination number of 6, an octahedral geometry is normally

assumed. On the other hand, when Pt has a coordination number of 4, a square planar
geometry is observed. A coordination compound has the empirical formula PtBr(en)
(SCN)2 and is diamagnetic. In aqueous solution, each unit of this compound produces
two complex ions. The ligand ethylenediamine (en) is present only in the cation while
Br is present only in the anion. (a) What is the molecular formula of this compound
(b) What is the formula of the complex cation ? (c) the complex anion ? (d) Give the
d-electron configuration (using Crystal Field Theory) of the Pt in each of the complex
ions.

5. The octahedral structure is not the only possible six-possible coordinate structure.
One possibility is a planar hexagonal structure, with the metal occupying the central
position and with a ligand at each corner of the hexagon. Show that the existence of
two and only two isomers of [Co(NH3)4Cl2]+ provides evidence against the hexagonal
structure.

6. The equilibrium constants (formation constants) for two nickel complexes are
shown below:
[Ni(H2O)6]2+(aq) + 6NH3(aq) --> [Ni(NH3)6]2+(aq) + 6H2O(l) Kf = 4 x 108
[Ni(H2O)6]2+(aq) + 3en(aq) --> [Ni(en)3]2+(aq) + 6H2O(l) Kf = 2 x 1018
Although the donor atom is nitrogen in both instances, the formation constants are
very different. With (en), it is ten orders of magnitude bigger. The generally larger
formation constants for polydentate ligands is called the chelate effect. Explain this
effect using a concept you have seen earlier in this course.

7.
(a) Draw all the geometric isomers for an MA 2B4 complex.
(b) Draw all the geometric isomers for an MA 2B2 complex in a planar arrangement.
For a tetrahedral arrangement, are geometric isomers possible?
(c) Draw all the geometric isomers for an MA 3B3 complex.

(d) Draw all the geometric isomers for an MABCD complex in a planar arrangement.
Are optical isomers possible?
(e) Draw all the geometric isomers of [Cr(en)(NH 3)2BrCl]+. Which of these isomers
also has an optical isomer? Draw the various isomers.

8. The following reduction potentials are known for various 3+ first-row transition
metal ions in aqueous solution:
Mn3+(aq) + e- --> Mn2+(aq) Eo=1.51 V
Fe3+(aq) + e- --> Fe2+(aq) E0=0.77 V
Co3+(aq) + e- --> Co2+(aq) E0=1.84 V
Explain why the reduction potential for Fe3+ is abnormally low.

9. [NiCl4]2- is more likely to be tetrahedral while [Ni(CN) 4]2- is more likely to be

square planar. Explain.

10. A Cu electrode is immersed in a solution that is 1.00 M in [Cu(NH 3)4]2+ and 1.00M
in NH3. When the cathode is a standard hydrogen electrode, the emf of the cell is
found to be 0.08 V. What is the formation constant for [Cu(NH 3)4]2+?

End of problem set 10

Problem Set 10
1. Werner also studied the electrical conductance of aqueous solutions containing a
series of platinum(IV) complexes having the general formula Pt(NH 3)xCl4, where x is
an integer that varied from 2 to 6. His results can be summarized as:
Formula of Complex

Number of ions produced upon complete

dissociation

Pt(NH3)6Cl4

Pt(NH3)5Cl4

Pt(NH3)4Cl4

Pt(NH3)3Cl4

Pt(NH3)2Cl4

Assuming that Pt(IV) forms octahedral complexes, (a) write the formulas for the five
compounds based on the dissociation results, (b) draw three-dimensional sketches of
the complexes, (include isomers that are possible), and (c) name each compound.
(a)
Formula of Complex

Rewritten Formula (showing the

coordinating ligands)

Pt(NH3)6Cl4

[Pt(NH3)6]Cl4

Pt(NH3)5Cl4

[Pt(NH3)5Cl]Cl3

Pt(NH3)4Cl4

[Pt(NH3)4Cl2]Cl2

Pt(NH3)3Cl4

[Pt(NH3)3Cl3]Cl

Pt(NH3)2Cl4

[Pt(NH3)2Cl4]

(b) and (c):

with 4 Cl- as counterions, hexaammineplatinum(IV) chloride

with 3 Cl- as counterions, pentaamminechloroplatinum(IV) chloride

with 2 Cl- as counterions, tetraamminedichloroplatinum(IV) chloride

with 1 Cl- as counterion, triamminetrichloroplatinum(IV) chloride

diamminetetrachloroplatinum(IV)

2. Crystal Field Theory fails in explaining why a neutral ligand such as CO can cause
a very large crystal field splitting. Use Molecular Orbital Theory to explain why the
CO ligand leads to a higher crystal field splitting.
In Molecular Orbital Theory, the crystal field splitting is related to the difference
between the energy of the t2g and eg orbitals. The t2g orbitals are essentially
nonbonding and are composed of the dxz, dyz and dxy orbitals. The CO molecule
contains empty antibonding orbitals. These antibonding orbitals have the same
symmetry as the t2g orbitals and since they are empty, these additional overlap
(see figure below) will lead to a lowering in energy of the t 2g orbitals:

The t2g orbitals lower in energy but the eg orbitals (since they do not overlap with
the orbital) remain the same in energy, thus, leading to an increase in the
energy separation between the t2g and eg orbitals.

3. In a linear field (as experienced, for example, by the d electrons in [Ag(NH 3)2]+),
how would Crystal Field Theory arrange the d orbitals according to increasing energy.
(Hint: Take z as the unique axis)
With the two point charges along the +z and -z axis.
___ dz2
___ dxz ___ dyz
___ dxy ___ dx2-y2

4. When Pt has a coordination number of 6, an octahedral geometry is normally

assumed. On the other hand, when Pt has a coordination number of 4, a square planar
geometry is observed. A coordination compound has the empirical formula PtBr(en)
(SCN)2 and is diamagnetic. In aqueous solution, each unit of this compound produces
two complex ions. The ligand ethylenediamine (en) is present only in the cation while
Br is present only in the anion. (a) What is the molecular formula of this compound
(b) What is the formula of the complex cation ? (c) the complex anion ? (d) Give the
d-electron configuration (using Crystal Field Theory) of the Pt in each of the complex
ions.
(a) Both Br- and SCN- have a charge of negative 1, thus, for the molecule to be
neutral, Pt needs a +3 charge. However, this will not be correct since the molecule
is diamagnetic. Pt(III) has an odd number of electrons so Pt cannot be
diamagnetic if it has a charge of +3. Thus, we will need at least 2 Pt's per
molecule. This automatically agrees with the observation that two complex ions
are produced. One Pt will be +4, the other +2 (average is then 3). The molecular
formula is then Pt2Br2(en)2(SCN)4.
(b) and (c)
In the molecular formula above, from the number of ligands, one can count the
number of coordination available for the 2 Pt's. Remember, en is bidentate so
each one counts twice. 2 (from the 2Br) + 4 (from 2 en) + 4 (from 4SCN) = 10.
With 2 Pt's, this may be 5 for each Pt. A coordination number of 5, however, is
not popular among Pt complexes. The more likely solution is that one Pt has a
coordination of 4 (therefore, square planar) amd the other Pt having a
coordination of 6 (octahedral). To solve this problem further, we need to apply
Crystal Field Theory. A coordination number of 4 and a square planar geometry
(due to the nature of the splittings of the d orbitals in a square planar field) will
be preferred by a d8 central atom. A coordination number of 6 and an octahedral
geometry will be preferred by a d6 central atom (provided that the ligands are
strong field ligands). Pt(II) is d8 and, thus, will be square planar, Pt(IV) is d6 and,
thus, will be octahedral. Pt(II) will be in the complex anion and Pt(IV) will be in
the complex cation.
Cation: [Pt(en)2(SCN)2]2+
Anion: [Pt(Br)2(SCN)2]2- (cis- and trans- isomers possible)
(d)

5. The octahedral structure is not the only possible six-possible coordinate structure.
One possibility is a planar hexagonal structure, with the metal occupying the central
position and with a ligand at each corner of the hexagon. Show that the existence of
two and only two isomers of [Co(NH3)4Cl2]+ provides evidence against the hexagonal
structure.

6. The equilibrium constants (formation constants) for two nickel complexes are
shown below:
[Ni(H2O)6]2+(aq) + 6NH3(aq) --> [Ni(NH3)6]2+(aq) + 6H2O(l) Kf = 4 x 108
[Ni(H2O)6]2+(aq) + 3en(aq) --> [Ni(en)3]2+(aq) + 6H2O(l) Kf = 2 x 1018
Although the donor atom is nitrogen in both instances, the formation constants are
very different. With (en), it is ten orders of magnitude bigger. The generally larger
formation constants for polydentate ligands is called the chelate effect. Explain this
effect using a concept you have seen earlier in this course.
When a solvent is bound as a ligand to a transition metal ion, it loses a great
degree of freedom. The degree of randomness or entropy depends heavily on the
number of free molecules. When a chelating agent binds to a metal ion, it
liberates more than one ligand thereby increasing the number of free molecules
and, consequently, the entropy of the system.

7.

(a) Draw all the geometric isomers for an MA 2B4 complex.

For complexes that have six ligands, we will assume octahedral geometry.

(b) Draw all the geometric isomers for an MA 2B2 complex in a planar arrangement.
For a tetrahedral arrangement, are geometric isomers possible?

Geometric isomers are not possible in a tetrahedral arrangement because all of

the corners of a tetrahedron are adjacent to one another.
(c) Draw all the geometric isomers for an MA 3B3 complex.

(d) Draw all the geometric isomers for an MABCD complex in a planar arrangement.
Are optical isomers possible?

Optical isomers are not possible for square planar complexes because any planar
compound will have a mirror plane containing all the atoms and a disymmetric
molecule cannot have a mirror plane of symmetry.
(e) Draw all the geometric isomers of [Cr(en)(NH 3)2BrCl]+. Which of these isomers
also has an optical isomer? Draw the various isomers.

I, II, IIIa and IVa are geometric isomers; I and II have mirror planes, thus, they
do not have optical isomers. IIIa/IIIb and IVa/IVb are the pairs of optical
isomers.

8. The following reduction potentials are known for various 3+ first-row transition
metal ions in aqueous solution:
Mn3+(aq) + e- --> Mn2+(aq) Eo=1.51 V
Fe3+(aq) + e- --> Fe2+(aq) E0=0.77 V
Co3+(aq) + e- --> Co2+(aq) E0=1.84 V
Explain why the reduction potential for Fe3+ is abnormally low.
H2O is a weak-field ligand, thus, in all the hexaaqua octahedral species of the
above ions, the metal is in a high-spin state. Mn3+ is d4, Fe3+ is d5, Co3+ is d6. Only
Fe3+ has all its d orbitals half-filled which is a relatively stable electronic
configuration. Thus, the reduction potential of the Fe(III) ion is less than its
neighbors in the periodic table.

9. [NiCl4]2- is more likely to be tetrahedral while [Ni(CN) 4]2- is more likely to be

square planar. Explain.
One advantage a tetrahedral arrangement has over a square planar one is space.
For this reason, most first row transition metals prefer tetrahedral while the
second and third-row transition metals prefer square planar. Square planar is
preferred because of the higher splitting of the dorbitals which is advantageous
when the metal ion does not have filled d orbitals. The Crystal Field Stabilization
Energy (CFSE) derived from the splitting of the d orbital energies is greater for
square planar arrangement. In a tetrahedral arrangement, no pair of ligands is
pointing at one specific d orbital. Thus, for first-row atoms such as Ni2+ (a
d8 species), tetrahedral arrangement will be preferred if the ligands are large and
weak-field. If the ligands are small (more rod-like) and are strong-field, the
planar arrangement will be preferred. The chloride ion is large and it is a weakfield ligand so tetrachloronickelate(II) is tetrahedral. The cyanide ion is small
and it is a strong-field ligand so tetracyanonickelate(II) will probably be square
planar.

10. A Cu electrode is immersed in a solution that is 1.00 M in [Cu(NH 3)4]2+ and 1.00M
in NH3. When the cathode is a standard hydrogen electrode, the emf of the cell is
found to be 0.08 V. What is the formation constant for [Cu(NH 3)4]2+?
The process is:
(A) 2H+(aq) + Cu(s) + 4NH3(aq) --> H2(g) + [Cu(NH3)4]2+
E = E0 - RT/nF (ln Q)
Q = 1; E = E0 = 0.08 V
The above process (A) can be written as (I+II+III):
I. 2H+(aq) + 2e- --> H2(g)
II. Cu(s) --> Cu2+(aq) + 2eIII. Cu2+(aq) + 4NH3(aq) --> [Cu(NH3)4]2+(aq)
The reduction potentials relate to each other:
EA = EI + EII + EIII
EA is known from the experiment, 0.08 V.
EI is 0.00 V (hydrogen reference)
EII is -0.337 V (the negative of the standard reduction potential of Cu(II))
Thus, EIII should be 0.417 V.
E0 = (0.0592/2) log Kf
log Kf = 2 (0.417)/0.0592
Kf = 1.2 x 1014

End of problem set 10