The Transition Metals

• d electrons in group 3 are readily removed via ionization.

• d electrons in group 11 are stable and generally form part of the core electron
configuration.
 Electronegativity

Electronegativity (χ
χ) is a chemical property that describes the ability of an atom to
attract electron density towards itself in a covalent bond.

• The electronegativity is dependent on the hybridization of the atom.

s orbitals experience stronger nuclear charge than p orbitals of same principal
quantum number, therefore χ(C) increases with higher s character of hybrid
orbital:

χ(Csp3) = 2.5; χ(Csp2) = 2.9; χ(Csp)= 3.95

[note: values may vary dependent on method of calculation]

χ of an element increases with increasing oxidation number of that element

e.g., χ(FeIII) > χ(FeII)

• The electronegativity of the elements increases substantially in progressing from left to
right (early to late transition metals) across the periodic table
– increased penetration effect (stronger effective nuclear charge)
• The electronegativity of main group elements increases in progressing up a column
– decreased shielding effect (stronger effective nuclear charge)
• The electronegativity of transition metal elements increases in progressing down a
column
- poor shielding from diffuse d orbitals
χM = (IP + EA)/2

• Ionization energies decrease down a group and increase across a period

(metals have higher ionization energies than non-metals)
http://goldbook.iupac.org/Graphs/E01990.3.map.html
 Group electronegativity
• χ(M) only useful for purely M-L σ-bonding complexes.
• Characteristic bonding in transition metal complexes has exceptionally strong
effect on χ(LnM).
• Thus reactivity determined by influence of σ and π interaction on χ(M) orbitals.
• Group electronegativity e.g. χ(L5M) will vary depending on the ligand set

EN(L5M) increases with π acceptor (and decreasing π donor) strength of L.

• Must consider χ(LnM) as trends deviate from that predicted by χ(M) alone.
• Mulliken electronegativity – mean of ionization potential and electron affinity
(Volts)
χM = (IP + EA)/2
 Transition Metal Valence Orbitals

• nd orbitals

• (n + 1)s and (n + 1)p orbitals

• dx2-dy2 and dz2 (eg) lobes located on the axes

• dxy, dxz, dyz lobes (t2g) located between axes
• for free (gas phase) transition metals: (n+1)s is below (n)d in energy
(recall: n = principal quantum #).

• for complexed transition metals: the (n)d levels are below the (n+1)s and thus get
filled first. (note that group # = d electron count)

• for oxidized metals, subtract the oxidation state from the group #.
• orbitals oriented orthogonal wrt each other creating unique possibilities for ligand
overlap.
• Total of 9 valence orbitals available for bonding (2 x 9 = 18 valence electrons!)
• For an σ bonding only Oh complex, 6 σ bonds are formed and the remaining d orbitals
are non-bonding.
• It's these non-bonding d orbitals that give TM complexes many of their unique
properties
 Geometry of Transition Metals
Coordination Geometry – arrangement of ligands around metal centre

Valence Shell Electron Pair Repulsion (VSEPR) theory is generally not applicable to
transition metals complexes (ligands still repel each other as in VSEPR theory)

For example, a different geometry would be expected for metals of different d electron
count
[V(OH2)6]3+ d2
[Mn(OH2)6]3+ d4 all octahedral geometry !
[Co(OH2)6]3+ d6
Coordination geometry is, in most cases, independent of ground state electronic
configuration

Steric: M-L bonds are arranged to have the maximum possible separation around the M.

Electronic: d electron count combined with the complex electron count must be
considered when predicting geometries for TM complexes with non-bonding d electrons
e.g. CN = 4, d8 (16 e−) prefers square planar geometry
d10 (18e−) prefers tetrahedral geometry
 Coordination number

Coordination Number (CN)

– the number of bonding groups at metal centre

Influenced by:

Size of the central atom

Steric interactions between ligands

Electronic interaction between the central atom & the ligands

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• Coordination Number (CN) – the number of bonding groups at metal centre

Low CN favored by:
1. Low oxidation state (e− rich) metals.
2. Large, bulky ligands.

Although Pd(P(tBu)2Ph)2 is coordinatively

unsaturated electronically, the steric bulk
of both P(tBu)2Ph ligands prevents
additional ligands from coordinating to
the metal.

What is the d electron count for Pd?

12
 • Coordination Number (CN) – the number of bonding groups at metal centre

High CN favored by:
1. High oxidation state (e− poor) metals.
2. Small ligands.

Water oxidation by mononuclear Ru complex involving a 7 coordinate Ru(IV) species.

Muckerman & Thummel Inorg. Chem. 2008
13
 • CN # 1

Very rare

In(C6H3-2,6-(C6H2-2,4,6-iPr))

Haubrich S. T.; Power P. P. J. Am. Chem. Soc. 1998, 120, 2202-2203

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 • CN # 2

Relatively rare

η5-Cp)(CO)2MnIn(C6H3-2,6-(C6H2-2,4,6-iPr))
(η Oxidation state of Mn?

Do steric effects really play a part here?

Haubrich S. T.; Power P. P. J. Am. Chem. Soc. 1998, 120, 2202-2203
15
• CN # 2 contd.

Relatively rare, occurring mainly with +1 cations of Cu, Ag and Au

Coordination geometry is linear
e.g. [H3N-Ag-NH3]+, [NC-Ag-CN]-, [Cl-Au-Cl]-

Oxidation state of Ag?

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• CN # 3

CN of three is extremely rare

[HgI3]- , K[Cu(CN)2] in the solid state.

ions are arranged at the corner of a distorted triangle.

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• CN # 3 contd.

The use of the very bulky bis(trimethylsilylamido) ligand has allowed the
characterization of Ce(III) in the coordination number 3.

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• CN # 4

Tetrahedral or square planar geometries

Commonly found for electron rich transition metals

e.g. AlCl4- Ni(CO)4 Ni2+,Pd2+,Pt2+,Rh+

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• CN # 4 contd.

tetrahedral geometry is preferred for d0 or d10

Oxidation state of Ti?

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• CN # 4 contd.

d8 electron configuration usually leads to square planar geometries

(as only one d-orbital required for forming the 4 metal ligand s-bonds)

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• CN # 5

Trigonal bipyramidal and square pyramidal exist

This geometry is less common than 4 and 6.

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• CN # 5 contd.

Iron pentacarbonyl
very toxic !!!

(DABCO)Fe(CO)4
[DABCO = 1,4-diazabicyclo[2.2.2]octane]

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• CN # 5 contd.

{FeCl[tBuN(SiMe2)]2O}2

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• CN # 5 contd.

Square pyramidal is less common

{acetatoaqua[[(4-methylimidazol-5-yl)methylene]histamine]-copper(II)} perchlorate

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• CN # 6

Octahedral….by far the most common geometry for transition metal complexes

The 6 ligands occupy the 6 vertices of an octahedron, which allows them to

minimize their M−L bonding distances, while maximizing their L· · ·L
nonbonding distances.

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• CN # 6

Octahedral

[chelate effect: multidentate ligands increase formation constant and

increase stability of complex]

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Correlation of coordination number and coordination geometry
for transition metal complexes.
 Crystal Field Theory
Describes how the d orbitals of the transition metal are affected
by the presence of coordinating ligands.

• Imagine the metal ion isolated in space,

then the d orbitals are degenerate.
• As the ligands approach the metal from the
six octahedral directions ±x, ±y, and ±z, the
degeneracy is broken
• The d orbitals that point toward the L
groups (dx2−y2 and dz2 ) are destabilized
by the negative charge of the ligands and
move to higher energy.
• Those that point away from L (dxy, dyz, and
dxz) are less destabilized.
• The crystal field splitting energy (∆
∆ - sometimes labeled 10Dq) depends on the value
of the effective negative charge and therefore on the nature of the ligands.
• Higher ∆ leads to stronger M−L bonds.
 High spin vs. low spin electron configuration
• If Δ is low enough, electrons may rearrange to give a "high spin" configuration to
reduce electron- electron repulsion that happens when they are paired up in the
same orbital.
• In 1st row metals complexes, low-field ligands (strong π - donors) favor high spin
configurations whereas high field ligands (π-acceptors/ strong σ donors) favor low
spin.
• The majority of 2nd and 3rd row metal complexes are low-spin irrespective of
their ligands.
• Low-oxidation state complexes also tend to have lower Δ than high-oxidation
state complexes.
• High oxidation state→ increased χ →increased Δ → high-spin configuration
 The 18-valence electron rule

“thermodynamically stable transition-metal complexes are formed when the sum of

the metal d electrons plus the electrons conventionally regarded as being supplied
by the ligand equals 18.”

• The 18 valence electron (18VE) rule introduced in 1927 by Sidgwick is based on the valence
bond (VB) formalism of localized metal-ligand bonds.

• The transition metal formally attains the electron configuration of the subsequent noble gas
in the periodic table.

• 18VE rule aka

inert-gas rule

effective atomic number (EAN) rule

Common oxidation states
 Electron Counting
• Organic compounds obey the octet (or 8 electron) rule:

C + 4H = CH4
(4 valence e−) + [4 x(1 valence e−)] = 8e−

• An octet is appropriate for carbon, where one 2s and three 2p orbitals make up
the valence shell; 8e− fill four orbitals.
• Transition metal complexes follow the 18 electron rule, appropriate for an atom
having 9 valence orbitals,
e.g. a first row transition metal has one 4s, three 4p and five 3d valence orbitals:

Cr0 + 6CO = Cr(CO)6

(6 valence e−) + [6 x(2 valence e−)] = 18e−
• First row transition metal carbonyls mostly obey the 18VE rule:

• Each metal contributes the same number of electrons as its group number.

• Odd electron metals attain 18 valence electrons through formation of M−M (Mn)
bonds or through reduction.
 Ionic vs. covalent model

• Both the covalent model and the ionic model differ only in the way the electrons
are considered as coming from the metal or from the ligands
- emphasize model…not a true representation of metal charge!!!
• Each model is often invoked without any warning in the literature therefore it is
important to be able to identify their use.
• The ionic model is most commonly used for traditional M−L inorganic
coordination compounds therefore coordinating ligands are treated equally in
both models.
• The ionic model is more appropriate for high-valent metals with N, O or Cl ligands.
• In the ionic model the M−X bond is considered as arising from a cationic M+ and
an anionic X− (heterolytic)
• The covalent model is sometimes preferred for organometallic species with low-
valent metals where the metal and ligand oxidation states cannot be
unambiguously defined.
• In the covalent model the M−X bond is considered as arising from a neutral metal
and ligand radical X• (homolytic).
• Consider the case of carbon tetrachloride CCl4

covalent model:

C + 4Cl = CCl4

(4 valence e−) + [4 x (1 valence bonding e−)] = 8e−

ionic model:

C4++ + 4Cl− = CCl4

(0 valence e−) + [4 x (2 valence bonding e−)] = 8e−

• Now consider the case of the metal hydride complex Mn(CO)5H

covalent model:

Mn + 5CO + H = Mn(CO)5H

(7 valence e−) + [5 x (2 valence bonding e−)] + (1 valence e−) = 18e−

ionic model:

Mn+ + 5CO + H− = Mn(CO)5H

(6 valence e−) + [5 x (2 valence e−)] + (2 valence e−) = 8e−

• Multidentate or chelating ligands can contribute multiple e-pairs:

Monodentate: pyridine 2e−

Bidentate: 2,2’-bipyridine 4e−

Monodentate: PPh3 2e−

Bidentate : dppe 4e−

• Bridging ligands contribute equally to both metals:

Bridging 4,4’-bipyridine 2 x 2e−

Terminal CO: CO 2e−
Singly bridging CO: μ2-CO 2 x 1e−

Terminal O2 O2 4e−
Bridging O2 μ2-O2 2 x 2e−

* Side-on CO can act as 4e− or even 6e− donor

* Bridging halides act as 4e donors (2 x 2e−)
• When applying the 18VE rule the following should be considered

1. The intramolecular partitioning of the electrons has to ensure that the total
charge of the complex remains unchanged (ionic or covalent model).

2. A M−
−M bond contributes one electron to the total electron count of a single
metal atom.

3. The electron pair of a bridging ligand donates one electron to each of the
bridged metal atoms.
1. The intramolecular partitioning of the electrons has to ensure that the total
charge of the complex remains unchanged.

2− + 2+ = 0
2. A M−
−M bond contributes one electron to the total electron count of a single
metal atom.

What is the d electron count of Mn in the unstable (CO)5Mn monomer?

3. The electron pair of a bridging ligand donates one electron to each of the
bridged metal atoms.