Zumdahl Chapter 20: Transition Metals and Coordination Chemistry

20.1: The Transition Metals – A Survey

General Properties
Transition metals show great similarities within a given period as well as within a given
vertical group
The last electrons added to these elements are inner electrons – do not participate as
readily in bonding
Exhibit metal behavior – metallic luster, high electrical/thermal conductivities
Properties vary considerably
Forming ionic compounds with nonmetals
More than one oxidation state
Complex ions: the transition metal ion is surrounded by a certain number of ligands
(molecules or ions that behave as Lewis bases).
Colored due to the absorption of visible light of specific wavelengths
Paramagnetic (unpaired electrons)
Electron Configurations
3d orbitals fill after 4s orbitals are full
Cr [Ar]4s1 3d5 is an exception
The energy of the 3d orbitals in transition metal ions is significantly less than that of the 4s
orbital
Remaining electrons occupy 3d orbitals since they are lower in energy
First row transition metal ions do not have 4s electrons
Oxidation States and Ionization Energies
First five metals the maximum possible oxidation state corresponds to the loss of all the 4s
and 3d electrons
Right end of PT
Higher oxidation states are not seen because the 3d orbitals become lower in energy as
the nuclear charge increases, making the e- increasingly hard to remove
Ionization energy gradually increases L to R across the period
Third ionization energy increases faster than the first ionization energy
Indicates decrease in energy of 3d orbitals going across the period
Standard Reduction Potentials
When metal acts as a reducing agent: M  Mn+ + ne-
Reverse of conventional listing
Metal with the most positive potential is the best reducing agent
All metals except copper can reduce H+ ions in 1M aw solutions of strong acid to H gas
Reducing ability decreases going L to R across the period
Cr and Zn do not follow trend
The 4d and 5d Transition Series
General decrease in size going from L to R across each series
4d and 5d are very similar in size due to lanthanide contraction
Differences between 4d and 5d increase from L to R
20.2: The First-Row Transition Metals
Scandium
Rare, +3 oxidation state, colorless, diamagnetic.
Titanium
Low density/high strength, white pigment in paper (TiO2)
Usually +4 oxidation state
Vanadium
Used in alloys with other metals
Usually +5 oxidation state (ranges from +5 - +2)
Chromium
Hard/brittle, tough oxide coating
Oxidation state of +2, +3 or +6
+2 is a powerful reducing agent in aqueous solution
+6 is a good oxidizinf agent
Manganese
Used for the production of especially hard steel
Oxidation state ranges from +2 - +7; +2 and +7 are most common
+7 is a strong oxidizing agent
Iron
Most abundant heave metal
White, lustrous, not particularly hard and very reactive toward oxidizing agents
Oxidation states of +2 and + 3
Cobalt
+2 and +3 oxidation states; others are known
Nickel
High electrical and thermal conductivities; resistant to corrosion – used for plating/alloys
Copper
High electrical conductivity, resistant to corrosion
Not highly reactive, but corrodes in air to produce green color
+2 oxidation state
Zinc
White lustrous, very active metal, good reducing agent
+2 oxidation states

20.3: Coordination Compounds

Usually colored and often paramagnetic
Complex ion (transition metal ion with its attached ligands) and counter ions (anions or
cations needed to produce a compound with no net charge).
Behaves like an ionic solid when dissolved in water
Primary valence (the ability of the metal ion to form ionic bonds with oppositely charged
ions) is called the oxidation state.
Secondary valence (the number of ligands or the number of bonds formed between the metal
ion and the ligands in the complex ion) is called the coordination number.
Coordination Number
Number of bonds formed varies from 2 to 8
Depends on size, charge and e- configuration
 6 is most common, and then 4
6 – octahedral arrangement; 4 – tetrahedral or square planar arrangement
Metal ions can show more than 1 CN
Ligands
A neutral molecule or ion having a lone pair that can be used to form a bond to a metal ion.
Lewis Definitions
Acid – electron pair acceptor
Base – electron pair donor
A ligand donates an e- pair to an empty orbital on a metal ion, the ligand is the lewis base
and the metal ion is the lewis acid.
Coordinate covalent bond
Monodentate ligand or unidentate ligand: a ligand that can form one bond to a metal ion
Chelating ligants or chelates: ligands with more than one atom with a lone pair that can be
used to bond to a metal ion
Bidentate ligand: a ligand that can form 2 bonds to a metal ion
Plydentate ligands: ligands that can form 2 + bonds to a metal ion
Nomenclature
Rules for naming coordination compounds
• The cation is named before the anion
• The ligands are named before the metal ion
• In naming ligands, an o is added to the root name of an anion.
o The halides as ligands are fluoro, chloro, bromo and iodo
o For a neutral ligand the name of the molecule is used
• The prefixes mono, di, tri, tetra, penta and hexa are used to denote the number of
simple ligands. The prefixes bis, tris, and tetrakis are used after those.
• The oxidation state of the central metal ion is designated by a roman numeral in
parenthesis
• When more than one type of ligand is present, ligands are named in alphabetical
order
• If the complex ion has a negative charge, the suffix –ate is added to the name of
the metal.

20.4: Isomerism
Isomers: two or more species with the same formula by different properties.
Structural Isomerism: isomers contain the same atoms but one or more bonds differ.
Stereoisomerism: all of the bonds in the isomers are the same by the spatial arrangements of
the atoms are different.
Structural Isomerism
Coordination isomerism: composition of the complex ion varies.
Linkage isomerism: the composition of the complex ion is the same, but the point of
attachment of at least one of the ligands differs.
Stereoisomerism
Have the same bonds but exhibit different spatial arrangements of their atoms
Geometrical isomerism or cis-trans isomerism: occurs when atoms or groups of atoms can
assume different positions around a rgid ring or bond.
Cis isomer: molecules are next to each other.
 Trans isomer: molecules are across from each other.
Optical isomerism: isomers have opposite effects on plane-polarized light.
Chiral: objects that have nonsuperimposable mirror images.

20.5: Bonding in Complex Ions: The Localized Electron Model

VSEPR model does not work for complex ions
Interactions between a metal ion and a ligand can be viewed as a Lewis acid-base reaction
Ligand donates a lone pair of electrons to an empty orbital on the metal ion to form a
coordinate covalent bond
Octahedral orbitals – hybridization of two d, one s and three orbitals to give six d2sp3 orbitals
Tetrahedral arrangement – sp3 hybrid
Square planar – dsp2 hybrid
Linear – sp hybrid

20.6: The Crystal Field Model

Focuses on the energies of the d orbitals
Assumes ligands approximated by negative point charges ; metal-ligand bonding is entirely
ionic
Octahedral Complexes
Negative point charge ligands repel negatively charged electrons, therefore the electrons will
prefer the d orbitals farthest from the ligands
dxz, dyz, and dxy orbitals (t2g) are at a lower energy than the dz2 and dx2-y2 orbitals (eg set)
The negative point charge ligands increase the energies of all the d orbitals.
Orbitals that point at the ligands are raised in energy more than those that point between
the ligands.
Splitting of the 3d orbital energies (delta) explains the color and magnetism of complex
ions of the first-row TM
Strong-field case (low-spin case): the electrons will pair in the lower energy t2g orbitals
(minimum number of unpaired electrons)
Diamagnetic
Weak-field case (high spin case): the electrons will occupy all 5 orbitals before pairing
occurs. (maximum number of unpaired electrons).
Paramagnetic
Spectrochemical series: order of ability to produce d-orbital splitting.
The magnitude of delta for a given ligand increases as the charge on the metal ion increases.
When a substance absorbs certain wavelengths of light in the visible region, the color of the
at substance is determined by the wavelengths of visible light that remain
Substance exhibits a color complementary to those absorbed
Delta E = hc/wavelength
Ligands determine size of d-orbital splitting, therefore color changes as the ligands change
Other Coordination Geometries
None of the 3d orbitals points at the ligands in the tetrahedral arrangement
Do not change d orbitals as much as octahedral arrangement
Delta tetrahedral = (4/9)delta octahedral
dxz, dyz, and dxy orbitals (t2g) are closer to point charges
d-orbital splitting is opposite to that for octahedral arrangement
 d-orbital splitting is small – weak field case (high spin) case always applies
Square planar
Start with octahedral arrangement and remove 2 point charges along z axis
Linear
Remove four point charges in xy plane

20.7: The Molecular Orbital Model

Most realistic view of bonding in complex ions
Extent of orbital overlap
Must have a net overlap in space to form MOs.
MOs formed when the ligands point at the lone pair orbitals
Relative orbital energies
AOs close in energy will interact more strongly than those widely separated in energy
General complex ML6n+
Bonding MOs are lower in energy than the ligand orbitals and metal ion orbitals that mix
to form them
Responsible for the stability of the complex ion
tg2 set that do not overlap w/ the ligand orbitals remain unchanged
Nonbonding orbitals
eg* MOs are antibonding orbitals
Higher energies therefore they destabilize the complex ion
Primarily composed of dz2 and dx2-y2 orbitals
Orbital energies not changed much by complex ion formation
Model accounts for d-orbital splitting in octahedral complexes
Accounts for magnetic and spectral properties of the species

20.8: The Biological Importance of Coordination Complexes

Most of first-row TM are essential for human health
Iron
Principal electron transfer molecules in the respiratory chain are iron-containing species
called cytochromes containing an iron complex called heme and a protein
Participates in transfer of electrons from nutrients to oxygen
Transports and stores oxygen in blood and tissues
Myoglobin: molecule that stores oxygen
Hemoglobin transfer O2 in the blood; molecule consists of 4 myoglobin-like units
Can bind 4 O2 molecules to form a bright red diamagnetic complex
O2 is a strong field ligand toward Fe2+
CO (toxic)
Affinity for Fe2+ in hemoglobin 200x greater than O2
Deprives the body of oxygen
CN- (toxic)
Prevents the e- transfer process; cases rapid death.
Respiratory inhibitor