General Chemistry II

Chapter 22 Lecture Notes

Transition Metal Chemistry

Introduction

The presence of partially filled d subshells in transition elements results in many

interesting chemical, spectral and magnetic properties.

What is the origin of the term transition?

The first transition series arises from filling the 3d shell.

The second transition series arises from the filling of the 4d shell, etc.

The lanthanides (4f) and the actinides (5f) are also sometimes considered transition
elements.

Properties of the Transition Metals

The first transition series, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn. Ten first transition
series elements in all.

Zn has a completely filled d shell but may still be considered a transition element due to
its position.

Transition elements are all metals; all form cations, conduct electricity and have shiny
surfaces.

General Physical Properties

Most transition metals have strong interatomic bonding so the pure metals have high
melting points, high heats of fusion and high densities.

Unlike iron, most resist corrosion due to strongly adherent oxide coatings (like Al).

Chromium, nickel and copper are used as decorative metals.

Electron Configurations

Most transition metals have multiple oxidation states that are not easily predicted by their
distance from the preceding noble gas electron configuration. .

Stable ionic charges can be rationalized on the basis of the stability of various 4sn3dm
configurations.

Electrons are most easily removed from the 4s shell.

The 3d5 and 3d10 configurations are especially stable.

For various reasons, the +2 state is stable in most first transition series metals (except Sc).

Only Mn has a +7 oxidation state (not ionic charge).

The highest oxidation states occur with oxygen in MnO4-1, CrO4-2, Cr2O7-2, etc.

Oxidation States

Common (already memorized) oxidation states include: Fe(II) and Fe(III).

Manganese has +2, +3 and +4 ions and higher (formal) oxidation states of +5, +6 and +7.

Copper has common states of +1 and +2.

Scandium only has +3, Zinc only has +2. Why?

Coordination Compounds

• Most metal cations have some tendency to form coordination compounds, even
nontransition metal ions such as Ca+2 and Al+3.
• Atoms or molecules called ligands act as Lewis bases and donate electrons to
metal cations which are always electron deficient, that is, have partially unfilled
orbitals.

• Common ligands include water, ammonia, halide ions, cyanide in, carbon
monoxide, thiocyanate, oxalate acetate, ethylenediamine and EDTA.
 • Transition metal ions have a greater tendency than other metals to accept bonds
from Lewis bases because of easily accessible, partially filled d orbitals.

• As an example, the compound CoCl3 · 6H2O is a is a coordination compound

where six water molecules are coordinated to the cobalt(III) ion and the chlorides
exist as counter ions only, not covalently bonded to the metal.

• Ligands such as water and ammonia are monodentate ligands.

• Ethylenediamine is bidentate, a chelating agent.

• EDTA is a tetradentate chelating agent.

• Citric acid is a tetradentate ligand used to inactivate calcium ion in blood to keep
it from clotting in collection tubes and bottles.

• The number of atoms bonded directly to the metal ion is its coordination number.

Metal Oxidation Numbers in Coordination Numbers

Ligands can allow some metal ions to exist in otherwise unstable oxidation states.

(Even zero and a few negative oxidation states are known.)

The oxidation number of a central metal ion is calculated from the charges on both the
coordinated and noncoordinated anions that surround the cation.

Ex: What are the coordination numbers and the oxidation numbers of the metals in the
following coordination complexes?

Ni(CO)4

[CoCl2(H2O)4]Cl

K3[Fe(CN)6]

K4[Fe(CN)6]

[Cu(NH3)2]Br2

[Pt(en)2Cl2]Cl2
Nomenclature of Coordination Compounds

Both ligand and metal ions naming is slightly different than in noncoordination
compounds.

Ligand Formula Common Name Ligand Name

Br-1 Bromide Bromo

Cl-1 Chloride Chloro

CN-1 Cyanide Cyano

OH-1 Hydroxide Hydroxo

O-2 Oxide Oxo

CO3-2 Carbonate Carbonato

NO2-1 Nitrite Nitro

C2O4-2 Oxalate Oxalato

NH3 Ammonia Ammine

CO Carbon monoxide Carbonyl

H2O Water Aquo

NH2CH2CH2NH2 Ethylenediamine Ethylenediamine

EDTA EDTetraacetate EDTetraacetato

Metal Name Metal Name in Anionic

Complex*

Aluminum Aluminate

Chromium Chromate

Cobalt Cobaltate

Copper Cuprate

Gold Aurate
 iron Ferrate

Lead Plumbate

Manganese Manganate

Molybdenum Molybdate

Nickel Nickelate

Silver Argenate

Tin Stannate

Tungsten Tungstate

Zinc Zincate

*Only one metal name is used, regardless of its oxidation state.

Rules for Naming Coordination Complexes:

• Most coordination compounds are ionic.. The complex ion can be either a cation
or an anion. Examples are Cu(NH3)2+2 and Fe(CN)6-3. Regardless of what the
complex ion is, the cation is always named first. But neutral complexes are also
known
• Within a complex ion, ligands are named first, in alphabetical order and the metal
ion last.
• The first table shows the names of ligands. The few neutral ligands listed such as
en keep their name. Common neutral ligands such as water, carbon dioxide and
ammonia use special names such as aquo, carbonyl and ammine. Anionic ligands
such as bromide, oxide and nitrite change to an -o suffix.
• Multiple ligands are indicated by Greek prefixes di-, tri-, tetra-, penta-, hexa-.
Complex ligands or any ligand already containing a Greek prefix use the prefixes
bis, tris and tetrekis.
• The oxidation number of the metal is written after the metal name with Roman
numerals in parentheses.
• If the complex is an anion, the metal name takes the -ate suffix. See Table.

Examples: Fe(CO)5 is pentacarbonyliron(0) or (iron carbonyl)

[FeSCN]((NO3)2 is thiocyanatoiron(III) nitrate

[Cr(H2O)6]Cl3 is hexaquochromium(III) chloride

K2CoCl4 is potassium tetrachlorocobaltate(II)

Fe3[Fe(CN)6]2 is iron(II) hexacyanoferrate(III) or ferrous ferricyanide

Fe2[Fe(CN)6] is iron(II) hexacyanoferrate(II) or ferrous ferrocyanide

Tetraamminedibromocobalt(III) nitrate is [Co(NH3)4Br2] NO3

Trisethylenediamineplatinum(IV) sulfate is [Pt(en)3] (SO4)2

Sodium tetranitrochromate(II) is Na2[Cr(NO2)4]

Coordination Compound Structures

The presence of six ligands around a metal ion makes possible different structural
isomers.

A coordination number of 2 produces linear structures.

Coordination number 4 gives the square planar structure.

Coordination number 6 gives the octahedral structure.

The square planar and octahedral structures can have different arrangements of ligands
called stereoisomers. Stereoisomers are compounds having the same number and types of
atoms bonded together but in different spatial arrangements. Stereoisomers have the same
molecular formulas but can have very different chemical and physical properties. Two
types of stereoisomers exist, geometric isomers and optical isomers.

Geometric Isomers

One type of geometric isomers called cis-trans isomers come in pairs where in one
isomer, a pair of groups is next to one another (cis). In the other (trans), the same two
groups are on opposite sides of a group or atom. A noncoordination example is the cis-
trans dichloroethene isomers. Other examples are the cis and trans isomers of
diamminetetrachlorocobaltate(III) ion and diamminedichloroplatinum(II).

Optical Isomers

Optical isomers are nonsuperimposable mirror images of each other. They have the same
physical (color, m.p., solubility) and chemical properties, except they rotate the plane of
polarized light in opposite directions. That was one of the first ways used to detect them.
Importance of optical isomers in organic and biochemistry.

Limited applicability of coordination chemistry.

Crystal Field Theory of Bonding in Coordination Compounds

There are two extreme views of interactions between transition metal ions and ligands. In
this context, crystal field theory addresses the effect of ligands on the d orbital energy
levels of the central metal ion only, not on the overall Born-Haber crystal lattice energy.

One view assumes overlap of the ligand's filled orbitals with the metal ion's partially
filled d orbitals. The other view assumes only electrostatic repulsion between filled
ligand orbitals and partially filled metal d orbitals. This gives a good understanding of the
spectral and magnetic properties of coordination compounds.

There are five d orbitals, dxy, dyz, dxz, dz2 and dx2 - y2, having equivalent energies in the
absence of a crystal field. In an octahedral crystal field, the lobes of the dz2 and dx2 - y2
orbitals are pointed directly at the six octahedrally-oriented ligand orbitals. The electrons
in those d orbitals will be repelled by the ligand electrons, making it harder for metal
electrons to enter those orbitals. On the other hand, the dxy, dyz, dxz orbitals are not
directly in line with the ligands and their energy is lowered. They experience less
repulsion from the electrons in the ligand orbitals. The result is a crystal filed splitting, ∆
which is the energy difference between the two subsets of orbitals. The magnitude of ∆
depends on the metal ion itself and the nature of the ligands. The energy difference, ∆ ,
influences the number of unpaired electrons in the metal ion (magnetic properties) and
the energy of spectral transitions (spectral properties, color) between the levels.

Colors of Coordination Compounds

The sensation of white light is caused by presence of all visible wavelengths striking the
eye. Color is the result of absorption of visible light by an object. Color is experienced
when certain wavelengths are absorbed and the remaining wavelengths are reflected to
the eye.

Colors of Visible Light Wavelengths

Perceived Color Wavelength

White 400 through 700 nm

 Red 650 to 700 nm

Orange 580 to 650 nm

Yellow 560 to 580 nm

Green 490 to 560 nm

Blue 430 to 490 nm

Violet 400 to 430 nm

The observed color of an ion comes from the wavelengths not absorbed. For instance,
absorption of yellow light gives a blue or violet color. Absorption of green light gives
red.

The Sc+3 ion is colorless because it has no d electrons to absorb visible light. The Zn+2
ion is colorless because it contains a filled shell, ten d electrons, so there can be no d-d
transitions.

Most other transition metal ions (hexaquo and other ligands) are colored because the
value of ∆ corresponds to the energy (hν ) of visible light photons. Most nontransition
metal ions are colorless because the ns and np electrons are held tightly, giving electron
transition energies in the (high energy) ultraviolet range.

The value of ∆ , the crystal field splitting, can be calculated to high precision for any
metal ion and any ligand by measuring the wavelength of light a complex absorbs.

Ex: Calculate the value of ∆ in J/atom and kJ/mol for the hexaquomanganese(II) ion
which has a pale pink color and absorbs light in the 570 nm (yellow) range?

For a single atom, E = ∆ = hν , where h is Planck’s constant. C = ν · λ

ν = C/λ = 2.998 x 108 m/s · 109 nm/m/570 nm = 5.26 x 1014 s-1

E = 6.63 x 10-34 J · s · 5.26 x 1014 s-1 = 3.49 x 10-19 J/atom = 210. kJ/mol

Ligands can be arranged in a Spectrochemical Series, a sequence depending on the

degree to which the split the crystal field. The Spectrochemical Series for the common
ligands is

I-1 < Br-1 < Cl-1 < OH-1 < F-1 < H2O < NH3 < en < CN-1 < CO

Carbon monoxide and cyanide are strong-field ligands because they produce large
splittings between the two sets of orbitals. A large ∆ leads to absorption of light in the
blue range of the spectrum and yellow ion colors. A small ∆ from the weak field halide
ligands absorbs the less energetic red photons and results in blue or green-colored ions.

Magnetic Properties of Coordination Compounds

The presence of unpaired electrons gives rise to the phenomenon of paramagnetism,

which makes a substance weakly attracted to a magnetic field (not to be confused with
much stronger ferromagnetism). The majority of substances have no unpaired electrons
and are weakly repelled by a magnetic field (diamagnetism). Unpaired electrons occur in
some transition metal complexes if they have an odd number of electrons or if the crystal
field splitting allows electrons to occupy orbitals without pairing up.

How many unpaired electrons will exist in low and high spin (high and low ∆ )
complexes for all the possible number of d electrons, one through ten?

1. For d1 (e.g. Ti+3), both high and low spin complexes have one unpaired electron.
2. For d2 (e.g. V+3), both high and low spin complexes have two unpaired electrons.
3. For d3 (e.g. Cr+3), both high and low spin complexes have three unpaired
electrons.
4. For d4 (e.g. Cr+2, Mn+3 ), high spin complexes have four unpaired electrons; low
spin complexes have two unpaired electrons.
5. For d5 (e.g. Mn+2, Fe+3), high spin complexes have five unpaired electrons; low
spin complexes have one unpaired electron.
6. For d6 (e.g. Fe+2), high spin complexes have four unpaired electrons; low spin
complexes have no unpaired electrons.
7. For d7 (e.g. Co+2), high spin complexes have three unpaired electrons; low spin
complexes have one unpaired electron.
8. For d8 (e.g. Ni+2), both high spin and low spin complexes have two unpaired
electrons
9. For d9 (e.g. Cu+2), both high and low spin complexes have one unpaired electron.
10. For d10 (e.g. Cu+1, Zn+2), both high and low spin complexes have no unpaired
electrons.

Tetrahedral and Square-Planar Complexes

In a tetrahedral arrangement the four ligands point directly at the dxy, dyz and dxz orbitals.
These become the high-energy orbitals and the dz2 and dx2 - y2 orbitals, which fit in
between, become the low energy orbitals. This reverses the energy level diagram from
that of the octahedral complexes. Since there are now four instead of six ligands, the
value of ∆ is less. Square planar ligands crate less predictable energy level splittings.
Reaction of Coordination Compounds

Two factors are important in the reactions of coordination compounds, the formation
constant, Kf and the speed at which reactions occur, or the Kinetic Lability of the
complex.

Many coordination complexes, especially the common, well-known ones have large Kf
values. Even so, some of them undergo rapid exchange of ligands. These are labile
complexes.

The Kf of the complex [Ni(CN)4]-2 is very high, but in the presence of excess cyanide ion,
cyanide in solution exchanges very rapidly with cyanide in the complex. This can be
shown by using radioactively labeled cyanide.

Other complexes are thermodynamically unstable in solution (small Kf) but may take
hours or days to decompose in aqueous solution, that is, have their ligands replaced by
water molecules..

Therapeutic Chelating Agents

Use of EDTA to complex Pb+2 and other heavy metals in blood and facilitate its removal
form the body by the kidneys.

Coordination Compounds in Chemical analysis

EDTA has great affinity for many +2 and +3 cations but the complexes are soluble and
not useful for gravimetric analysis. Dimethylglyoxime selectively forms a characteristic
red-brick precipitate with Ni+2 and is used to determine nickel from the mass of
precipitate produced.

Detergents

Use of tripolyphosphate ion forms a small amount of white, granular precipitate with
calcium in hard water. Used to prevent Ca+2 from precipitating soap anions to from gray
"soap scum".