Transition metal complexes

Part 1 outline
‹ Transition metals and their common oxidation
states
‹ What is a metal complex?
‹ Geometries of complexes
‹ Common ligands
‹ Isomerism in coordination complexes
‹ Naming transition metal complexes

1
Transition metal oxidation states
Sc Ti V Cr Mn Fe Co Ni Cu Zn
3 3,4 2, 3, 2, 3, 2, 3, 2, 3 2, 3 2 1, 2 2
4, 5 4, 6 4, 6, 7

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
3 4 3,4, 5 2,3,4, 2,3,4, 2,3,4, 1, 3 2, 4 1 2
5, 6 5,6,7 5,6,7,
8
La Hf Ta W Re Os Ir Pt Au Hg
3 4 3, 4, 5 2,3,4, 2,3,4, 3,4,5, 1, 3 2, 4 1, 3 1, 2
5, 6 5,6,7 6,7,8

These are “common” oxidation states. It is not supposed to be an exhaustive list.

Low oxidation states of heavy metals like Ta, Nb, Mo, W and Re tend be found in
compounds containing metal-metal bonds

Transition metal complexes

‹A transition metal complex is species a consisting of
a transition metal coordinated (bonded to) one or
more ligands (neutral or anionic non-metal species)
‹ Transition metal complexes are important in catalysis,
materials synthesis, photochemistry, and biological
systems
‹ Display diverse chemical, optical and magnetic
properties

2
 An example of a complex

Ligands

We can view the

complex as
ligands (Lewis Metal ion
bases) bound to
a metal ion (a
Lewis acid)

Coordination numbers
‹ Transition metal ions usually form complexes with a
well defined number of ligands
‹ Complexes with coordination numbers four and six
are the most common, although two and five
coordination are also very well established
‹ Coordination number and geometry are determined by
a combination of:
- Metal ion size
- Ligand size
- Electronic factors (electron configuration, ligand type)

3
Linear complexes
‹ Two coordinate linear
complexes are almost
exclusively found for
d10 metal ions
– Ag+, Hg2+ etc
– These metals can adopt
higher coordination
numbers under favorable
circumstances

Four coordination
‹ Four coordinate complexes
typically have a tetrahedral
or square planar geometry
‹ Square planar geometry is
only found when there are
electronic reasons for it
‹ Tetrahedral geometry is
often found for steric
reasons
– Small metal ion and large
ligands

4
Square planar complexes
‹ Square planar coordination is
rarely encountered for metals
that do not have a d8 electron
configuration
‹ For 3d metals this d8
configuration has to be
combined with a π acceptor
ligand, giving a large crystal
field splitting, to get square
planar coordination
‹ For 4d and 5d metals nearly
all d8 complexes are square
planar irrespective of the
ligand

Five coordinate complexes

‹ There are two common
geometries for five
coordinate complexes:
TBP and square pyramidal
– TBP is sterically favored
over square pyramidal
– Energetic difference
between the two geometries
is small
– Geometry can be dictated
by the use of an appropriate
ligand or by crystal packing
requirements

5
Six coordination
‹ By far the most
common six
coordinate geometry
is octahedral, but
various distortions of
the octahedral
geometry and
trigonal prismatic
coordination can be
found

Trigonal prismatic coordination

‹ Found in sulfide materials
such as MoS2 and in
complexes where the
ligand is small relative to
the metal center
(octahedral is sterically
favored over prismatic) or
where special ligands are
used
– Ligands with a small bite
angle tend to favor trigonal
prismatic coordination

6
Higher coordination numbers
‹ Someof the early transition metals are large enough to
accommodate more than six ligands
– 13-15 7-coordinate, 17-20 8-coordinate, 21 9-coordinate

Ligands
‹ Ligands are species (neutral or anionic)
bonded to the metal ion
‹ They may be attached to the metal through a
single atom (monodentate) or bound to the
metal through two or more atoms (bidentate,
tridentate etc.)
‹ Polydentate ligands are called chelating
ligands

7
Example simple ligands

Neutral Molecules Anions

Aqua H2O Fluoro F-
Ammine NH3 Chloro Cl-
Methylamine CH3NH2 Bromo Br-
Carbonyl CO Iodo I-
Nitrosyl NO Hydroxo OH-
Cyano CN-

List of common ligands

8
Example chelating ligands
O O O-

O O
O- O-
M O O- N O-

Ethylenediamine Oxalate acting

acting as a bidentate as a bidentate N
ligand ligand
O-
H2N H2N
CH2
O
H2C
NH2 NH2 Ethylenediaminetetraacetate
Note both of these drawing Can act as hexadentate ligand
imply the same thing

Ligands and oxidation state

‹ Low oxidation state complexes can be stabilized by
using ligands such as cyanide and carbon monoxide
(π acceptor ligands – see later for explanation)
‹ Intermediate oxidation state complexes often have
ligands such as chloride, ammonia or water
‹ High oxidation state complexes usually have fluoride
or oxide as ligands

9
Isomerism in metal complexes
‹ Isomers are compounds with the same chemical
formula but different structures
- Note that as they have different structures they will
have different physical and chemical properties

Geometrical isomers
‹ Geometrical isomers may exist as distinct compounds
because there is no low energy path for their
interconversion

MA4B2 octahedral compounds

MA2B2 square planar

compounds

Geometrical isomers have different

physical and chemical properties
MA3B3 octahedral compounds

10
Isomers of square planar complexes
‹ Different isomers can selectively prepared
and distinguished by a variety of methods
– Reactions are different
– 31P NMR spectra for cis and trans
PtClBr(PMe3)2 are different

Chirality
‹ Objects that are not superimposable on their
mirror images are said to be chiral
– e.g. left and right hand

11
Chiral molecules
‹ Molecules are not always superimposable on their
mirror images
- If a molecule and its mirror image are not
superimposable they are said to be chiral and they are
related to one another as enantiomers
> This is a type of isomerism – optical isomerism

Properties of chiral molecules

‹ Molecules that are related to one another as
enantiomers have the same boiling points, densities,
colors etc.
– However, they rotate plane polarized light in opposite
directions
– They react in different ways with other chiral molecules
‹ As most biological molecules are chiral, this implies
that living systems will deal in different ways with
species that are related as enantiomers
– One optical isomer of a drug may be beneficial the other
may be lethal

12
Optical rotation

Symmetry criteria for chirality

‹ Molecules that have inversion centers of
mirror planes are not chiral

13
Optical isomerism in metal complexes

‹ Any species that does not have an Sn axis is

chiral
‹ Common examples include compounds with the
formula ML3 where L is a bidentate ligand
‹ Even compounds with the formula MA2B2C2
can be optically active

Examples of optical isomerism

14
Naming enantiomers
‹d and l are used to denote which way a species rotates
plane polarized light (at a specific wavelength)
– when looking into the light source, d [or (+)] implies the
plane of polarization rotates clockwise
‹∆ and Λ are used to denote an absolute configuration
(the arrangement of atoms in space). You have to
know the structure of the isomer to assign the absolute
configuration
– Complexes with a ∆ absolute configuration do not always
rotate light in a d fashion. In fact the direction in which they
rotate the plane of polarized light depends on what
wavelength you use

∆ and Λ

To decide if a particular isomer

has a Lambda or Delta absolute
configuration look down the
molecular 3-fold rotation axis
and see if the ligand backbones
rotate to the left or the right as
they go away from you

15
Linkage isomerism
‹ Some ligands can link to a metal through one
of two or more different atoms
– NO2- can link through oxygen or nitrogen
» [Co(ONO)(NH3)5]+ and [Co(NO2)(NH3)5]+
– NCS- can link through S or N
– SO32- can link through O or S

Ionization and hydration isomerism

‹ Ionization isomerism
– [Co(NH3)5(Br)]SO4 versus [Co(NH3)5(SO4)]Br
– or [Pt(NH3)3(Cl)]Br versus [Pt(NH3)3(Br)]Cl
‹ Hydration isomerism
– [Cr(H2O)6]Cl3 versus [Cr(H2O)5Cl]Cl2.H2O versus
[Cr(H2O)4Cl2]Cl.2H2O

16
Isolation of isomers
‹ Isomers can only be isolated as pure species if there is
no easy pathway for the different isomers to
interconvert.
– For there to be no rapid interconversion pathway the ligand-
metal bonds must be quite non-labile (ligand should not be
able to “drop” off and then reattach somewhere else)
» Metal ions like Co3+, Cr3+, Pt2+ do not readily undergo ligand
exchange reactions so isomers containing these metal ions can often
be isolated
– The ligands should not be able to move around while still
attached to the metal center
» This is not usually a problem for coordination complexes, but in some
trigonal bipyramidal species axial and equatorial ligands can change
places with one another Fe(CO)5, PF5 etc.

Berry Pseudorotation
‹ Berry pseudorotation provides pathway for the
interconversion of different isomeric forms of a
trigonal bipyramidal species
– Axial ligand become equatorial ligands. Process goes via a
square based pyramidal intermediate

17
Isolation of enantiomers
‹ Separating a mixture of enantiomers into individual
components is called resolution
‹ The resolution of chiral metal complexes is typically
performed by crystallization
– If we use an optically pure chiral anion, the different salts
will be related as diastereomers and hence have different
solubilities
» This requires a source of optically pure resolving agent.
Typically, natural materials such as tartrate are used as they are
readily available in optically pure form.

Naming of complexes
‹ The naming of compounds containing coordination complexes
follows a set of well defined rules
- 1) In a salt, the cation is always named before the anion
- 2)The names of ligands are given in alphabetical order
> The names of coordinated anions end “o”, e.g. chloro, cyano etc.
> The names of neutral ligands are just the name of ligand molecule
> Some ligands have special names when they are in complexes eg. H2O – aquo,
NH3 – ammine
- 3) The number of ligands that present is indicated by a prefix, di, tri etc.
However, if these prefixes are already in the name of the ligand bis, tris,
tetrakis etc. are used instead
> Dichloro means two chloride ligands
> Bisenthylenediamine means two ethylenediamine ligands
- 4) After the ligands we specify the metal and its oxidation state as a roman
numeral in brackets
> Platinum(II) indicates that we have platinum in an oxidation state of two

18
Additional rules for naming complexes

‹ Ifwe have ambidentate ligands like SCN- we

specify the atom that is binding to the metal
- For example thiocyanato-S implies bound through
sulfur to the metal center
‹ Sometime a polydentate ligand will bridge
between two or metal centers. The notation µ –
is used to indicate that the ligand is bridging

Examples
‹ Name the following:

[Pt(NH3)4][PtCl4]

Trans-[CoCl(en)2(NCS)]Br

19
 Examples
‹ Draw structures for the following:

Tris(ethlyenediamine)cobalt(III)nitrate

Potassium dibromobis(oxalato)chromium(III)

Part 2 outline
‹ Bonding in transition metal compounds
- 18 electron rule
- Crystal field theory
- Molecular orbital approach
‹ High spin and low spin complexes
- Magnetic measurements
- High-spin low-spin equilibria
‹ Optical spectra
- d-d transitions for d1 ions and more complicated cases
- Spectrochemical series
- Charge transfer transitions
‹ Crystal Field Stabilization Energy (CFSE) and trends in ionic radii
‹ Jahn-Teller distortions

20
 18 electron rule
‹Stable low oxidation state complexes are found to have a
total of 18 bonding electrons
- metal electrons plus lone pairs from ligands
‹Ni(CO)4 - 4s23d8 and 4 lone pairs
‹Fe(CO)5 - 4s23d6 and 5 lone pairs
‹Cr(CO)6 - 4s23d4 and 6 lone pairs
‹The stability of these 18 electron species can be
explained using MO theory
- Corresponds to filling all the molecular bonding orbitals and none of the
antibonding orbitals
‹However, the 18 electron rule only works for species
with metals in a low oxidation state NOT FOR MOST
COMPLEXES

Bonding in coordination complexes

‹ There are two commonly used approaches to describing
the bonding in transition metal coordination complexes
– “Crystal Field Theory” and molecular orbital theory
‹ Crystal Field Theory is an electrostatic approach where
we treat the ligands as point negative charges and ask
ourselves what the effect of repulsion between these
charges and the d-electrons on the metal ions will be
– Explains many of the basic physical properties of transition
metal complexes but not all of them
‹ Molecular orbital theory is more complex than crystal
field theory, but it allows a more complete explanation of
the observed physical properties

21
 d-orbitals
‹ In an isolated gas phase atom or
ion, the five d-orbitals
associated with a given
principle quantum number are
degenerate
- That is they have the same
energy as one another

Crystal Field Theory

‹ Consider the ligands are point negative
charges or as dipoles. How do these charges
interact with the electrons in the d-orbitals?

22
Octahedral complexes
‹ Two of the d-orbitals point towards the ligands
– Repulsion between the ligand electrons and electrons in these two d-
orbitals destabilizes them

∆oct or ∆o is referred to as the ligand field splitting for

the octahedral complex

Colors
‹ The colors of most transition metal complexes arises
as a consequence of the ligand field splitting

23
 Ligand field splitting
‹ The ligand field splitting depends upon the metal, the
oxidation state of the metal, and the ligand type
‹ High oxidation state favors large ∆
– Mn2+ < Ni2+ < Co2+ < Fe2+ < V2+ < Fe3+ < Co3+ < Mn4+ <
Mo3+ < Rh3+ < Ru3+ < Pd4+ < Ir3+ < Pt4+
‹ Effect of ligand is given by the spectrochemical series
– I- < Br- < S2- < SCN- < Cl- < NO3- < F- < OH- < C2O42- < H2O
< NCS- < CH3CN < NH3 < en < bipy < phen < NO2- < PPh3 <
CN- < CO

Ligand field splitting parameters

24
Tetrahedral complexes
‹ Three of the d-orbitals point almost towards the ligands.
The other two point between the ligands
– Repulsion between the ligand electrons and electrons in the three
d-orbitals that almost point at the ligands destabilizes them

For a given ligand-metal combination, ∆tet should be smaller than

the ∆oct (4/9ths) as there are fewer ligands in the tetrahedral
complex and none of them point directly at the d-orbitals

d-orbitals in tetrahedral complexes

‹ In a tetrahedral complex the
degeneracy of the five d-
orbitals is broken to give two
degenerate “e” orbitals and
three degenerate “t2” orbitals
- While none of the orbitals point
directly at the ligands, some of
them (t2) are oriented so they
point more closely towards the
ligand positions and hence the
electrons in the t2 orbitals are
higher in energy than those in
the e orbitals

25
Tetragonal and square planar complexes
‹ If we distort an octahedral
complex, the degeneracy of the
eg and t2g orbitals is broken. As
the axial ligands are pulled
away from the metal a
tetragonal species is formed.
– The repulsions between the
ligands and the d-electrons are
different after the distortion.
This leads to a further loss of
orbital degeneracy
– In the extreme case where the
axial ligands are removed we
are left with a square planar
complex

MO theory
‹ Crystal field theory explains many
phenomena but not, for instance, the
spectrochemical series
- Why is CO such as strong field ligand (gives big
value of ∆)?
‹ MO theory offers a better qualitative picture

26
 Octahedral sigma bonded complex
‹ If the ligands in a
complex are only
capable of forming
bonds with the metal
using one lone pair from
each ligand, we have to
consider the following
ligand and metal orbitals
when constructing
molecular orbitals

Orbital energy level diagram for

a sigma bonded complex
‹ With the MO approach to
bonding in the complex, the
ligand field splitting ∆ is the
energy gap bewteen a set of
nonbonding orbitals (t2g) and
the lowest lying antibonding
orbitals (eg)
– As the interaction between the
ligand orbitals and the metal
orbitals gets stronger, the energy
difference between the eg
bonding and eg antibonding
orbitals in the complex gets
larger so ∆ also gets larger

27
Ligands that can form π bonds
‹ Many ligands have more than
one orbital that can interact with
the transition metal ion
– For example, halide anions have
lone pairs in p-orbitals lying
perpendicular to the metal ligand
axis. These p-orbitals can be
involved in bonding as they overlap
with some of the metal d-orbitals
– Molecules like CO and CN- have
empty orbitals (π*), that do not lie
along the metal-ligand axis, that
can also be involved in bonding to
the metal

π-donor ligands
‹ π-donor ligands (e.g. halide)
give smaller ∆’s because the
filled π symmetry ligand
orbitals interact with the t2g
symmetry orbitals on the metal
- This is why F-, Br- OH- are weak
field ligands (give small ∆’s)

28
π-acceptor ligands
‹ Ligands with empty
π- symmetry orbitals
e.g. CO give large D’s
because the empty
orbitals on the ligands
interact with the t2g
orbitals on the metal
and increase ∆.

Carbonyl complexes
Stable CO complexes are
only formed by metal
ions that are electron
rich. The metal has to
have electrons in its t2g
orbitals that can be
“donated” to the CO to
form a strong bond to the
CO

‹ Carbonyl ligands are strong π-acceptors

– backbonding (the interaction between the filled t2g orbitals on
the metal and the π∗ orbitals on the CO) weakens the C=O bond
as seen by vibrational spectroscopy
» The CO stretch frequency in a metal complex such as Ni(CO)4 is lower
than that for molecular CO

29
High spin and low spin complexes
‹ Octahedral complexes with d4, d5, d6, and d7 electron
configurations can in principle be in high or low spin
states

‹ If∆ is bigger than the energy required for spin

pairing the complex will be low spin

Factors effecting spin state

‹Both ∆ and the spin pairing energy depend upon the
metal and the ligands.
- High field ligands, CN- etc, high metal oxidation state, and
metals from the 4d and 5d series all favor large ∆ and hence
the formation of low spin complexes
‹Tetrahedral complexes can also in principle occur in
high and low spin forms.
- As ∆tet is always less than ∆oct, other things being equal,
nearly all tetrahedral complexes are high spin

30
High spin-low spin equilibria
‹ Some coordination
complexes show a phase
transition from high to
low spin as a function of
temperature
– This has been used as a N
N
means of information
storage for prototype phen
smart cards!
– Transition presumably
occurs because ∆ is
slightly temperature
dependent in the solid
state

Experimental methods for determining

the spin state
‹ The spin state of a complex influences both the
absorption spectrum and the magnetic properties of
the species
‹ Absorption spectra are usually harder to interpret than
magnetic data
‹ Both the orbital and spin angular momenta of the
electrons influence the magnetic properties of a
sample
- But in coordination complexes the orbital contribution can
often be ignored

31
 Measuring magnetic properties
‹ We can measure the magnetic properties
of a sample by hanging a vial of material
from a balance so that it sits partly in a
magnetic field
– The sample will be pulled down into the
magnet if it contains unpaired electrons (said
to be paramagnetic)
– It will tend to be pushed out of the field if it
contains no unpaired electrons (diamagnetic)
‹ The amount of material in the vial along
with the extent to which the sample is
pulled into the magnet allows us to
calculate the magnetic susceptibility of
the sample
– Sample with a high magnetic susceptibility is
strongly pulled into the magnetic field

Interpreting magnetic measurements

‹ The magnetic susceptibility (χ) is measured as a function
of temperature
‹ A magnetic moment (µ) for each metal ion can be
obtained from the magnetic susceptibility
- We can think of the unpaired electrons on each atom as behaving
like a little bar magnet. The magnetic moment of an atom or ion
is a measure of how strong this bar magnet is.
‹ Theoretically, for spin only systems µ = 2 [S(S +1)]1/2 µB
- µB (Bohr magneton) are the units in which the magnetic moment
is given
- S is the total spin angular momentum. It tells you how many
unpaired electrons there are
> S = 0.5n, where n is the number of parallel spin unpaired electrons in the
ion

32
 Spin only magnetic moments
Ion n S µ/µB µ/µB

Calculated Experimental

Ti3+ 1 ½ 1.73 1.7-1.8

V3+ 2 1 2.83 2.7-2.9

Cr3+ 3 1½ 3.87 3.8

Mn3+ 4 2 4.90 4.8-4.9

Fe3+ 5 2½ 5.92 5.9

There is reasonable agreement between calculated spin only magnetic

moments and those measured for many 3d metal complexes

Magnetic properties
‹ Magnetic susceptibility measurements can be used to
tell if a complex is high or low spin
‹ They can also be used to distinguish between square
planar and tetrahedral geometries. Square planar
complexes are nearly always low spin d8
(diamagnetic). If a four coordinate compound is
paramagnetic it is probably tetrahedral
- e.g. Ni(CN)42- (square planar) is diamagnetic, but NiCl42-
(tetrahedral) is paramagnetic

33
Electronic spectra
‹ TM complexes with more than one d-electron
often show absorption bands at multiple
wavelengths
– not just one transition corresponding to ∆
‹ The appearance of multiple bands is due to
electron-electron repulsion
– may have more than one state for a given electron
configuration

d2 complexes
‹ For complexes with more
than one d-electron there
are often several allowed
transitions

34
Charge transfer transitions
‹ Some transition metal complexes with no d-electrons
are colored
– This is because there can be electronic transitions in the
visible region that do not involved d-electrons
» MnO4- : electrons in filled oxygen based orbitals are excited into
empty d-orbitals. This type of Ligand to Metal Charge Transfer band
gives rise to the intense purple color of permanganate
» CrO42- : intense yellow color from LMCT band
– Metal to ligand charge transfer bands also occur in the visible
regions for some complexes
– Charge transfer transitions are often much more probable
than d-d transitions. Hence the intense color of MnO4-

Ligand field stabilization energies

‹ We can compute a quantity called the Ligand Field Stabilization
Energy (LFSE) by comparing the energy of the d-electrons in a
species with all five d-orbitals degenerate, to their energy in a
complex where the degeneracy of the orbitals has been broken
– This LFSE can be used to explain some of the properties of transition metal
ions

Example calculation: LFSE for

high spin d5 = [3 x (2/5∆) –
2x(3/5∆)] = 0
Strong field implies low spin. Weak field implies high spin

35
 Hydration energies
‹ The double humped trend that is seen in the hydration
enthalpies of TM ions can be explained using the
Ligand or Crystal Field Stabilization Energy
CFSE for high spin d4 is
= (+3/5 – 2/3 – 2/3 – 2/3)∆

Ionic radii for 3d metals

‹ For high spin ions
there is a “double
humped” trend in
ionic radii
– Due to crystal field
stabilization effects

36
 Lattice energies of 3d oxides MO

‹ Double humped
trend due to CSFE
and high spin ions

LFSE and coordination preferences

‹ The LFSE for octahedral and tetrahedral sites is
different and the magnitude of the difference varies
with d-electron configuration
– Some metal ions show a strong preference for octahedral
coordination due to LFSE effects

37
 Degree of inversion in Spinels
‹ AB2O4 materials with the Spinel structure have one tetrahedral
and two octahedral sites per formula unit
‹ The fraction of the A cations that are found in the octahedral sites
is referred to as the degree of inversion γ
– If all the A cations are octahedral the material is an inverse Spinel, and if
all the A cations are tetrahedral the Spinel is said to be normal
– Degree of inversion can be rationalized using CFSE arguments

Jahn-Teller effect
‹ Jahn-Teller theorem states that
any species with an electronically
degenerate ground state will
distort to remove the degeneracy
– Compounds containing
approximately octahedral Cu2+ (d9-
t2g6eg3), Mn3+ (d4 - t2g3eg1) and L.S.
Ni3+ (d7 - t2g6eg1) often display
distorted coordination
environments as the distortion
breaks the degeneracy of the
octahedral ground state

38
Jahn-Teller effect 2
‹ Typical distortion of an octahedron leads to 4 + 2
coordination with either 2 short or 2 long bonds
‹ JT effect important in copper oxide superconductors
and manganese CMR materials
‹ JT effect can also occur for tetrahedrally coordinated
species
‹ JT effect not very strong for “octahedral” compounds
with degenerate ground state involving incomplete
occupancy of t2g orbitals

Reactions of complexes
‹ Reactions of transition metal complexes typically involve the
replacement of one ligand by another (substitution) or
oxidation or reduction
– These reactions are all associated with a thermodynamic driving force
(∆G determines the equilibrium product distribution) and a rate.
‹ Thermodynamics of substitution reactions
– Formations constants
– Chelate effect
– Irving Williams order
‹ Kinetics of substitution reactions
– What factors influence the rate of a reaction?
– What mechanisms are important?

39
 Coordination equilibria
‹ Many complex formation reactions are solvent
displacements
‹ M(OH2)6 + L ==== M(OH2)5L + H2O
‹ These equilibria can be characterized by formation
constants
– M + L == ML K1 = [ML]/[M][L]
– ML + L == ML2 K1 = [ML2]/[ML][L]...
– Overall formation constant βn = K1K2K3..Kn
» βn is the equilibrium constant for M + nL == MLn
‹ The values of the equilibrium constants depend upon the
nature of the metal ion and the ligands

Trends in formation constants

‹ For MLn-1 + L == MLn, typically K1 > K2 > K3 > ... > Kn
– This can be explain on statistical grounds. The greater the number of
ligands that have already been substituted, the smaller the number of open
sites for additional substitution
Example data for Ni(II) amines:
Kn is equilibrium constant for [Ni(NH3)n-1(H2O)7-n]2+ + NH3 == [Ni(NH3)n(H2O)6-n]2+ + H2O
n pKn Kn/Kn-1
pKn and hence Kn Experimental Statistical
decrease as n goes
up as expected, and 1 -2.72
the ratios Kn/Kn-1 2 -2.17 0.28 0.42
are in approximate
agreement with 3 -1.66 0.31 0.53
those expected on 4 -1.12 0.29 0.56
statistical grounds
5 -0.67 0.35 0.53
6 -0.03 0.2 0.42

40
Statistical treatment of successive Kn
‹ Consider the following substitution reaction in an
octahedral complex
– MX7-nLn-1 + L == MX6-nLn + X
– The probability of the forward reaction should be
proportional to the number of X ligands available for
substitution in the starting material (7-n). The
probability of the reverse reaction should be
proportional to the number of L ligands available for
substitution in the product (n).
– Assuming that the enthalpy changes associated with
each substitution are the same
» Kn = (7-n)/n
» So Kn/Kn-1 = [(7-n)/n] [(n-1)/(8-n)]
‹ This formula gives the “statistical values” in the previous table

Effect of successive reactions

‹ As with polyprotic acids,
the successive replacement
of water by other ligands
can lead to a complex
mixture of species in
solution

[Cu(OH2)4]2+ + NH3 == [Cu(NH3)(OH2)3]2+ + H2O log K1 = 4.22

[Cu(NH3)(OH2)3]2+ + NH3 == [Cu(NH3)2(OH2)2]2+ + H2O log K2 = 3.50
[Cu(NH3)2(OH2)2]2+ + NH3 == [Cu(NH3)3(OH2)]2+ + H2O log K3 = 2.92
[Cu(NH3)3(OH2)]2+ + NH3 == [Cu(NH3)4]2+ + H2O log K4 = 2.18

41
 The Irving-Williams order
‹ The binding of a ligand to a metal depends
on the size of the ion, its charge, and the
hardness/softness of the donor and acceptor
atoms
‹ For alkaline earths and first row 2+ ions the
following trend is observed:
– Ba2+ < Sr2+ < Ca2+ < Mg2+ < Mn2+ <
Fe2+ < Co2+ < Ni2+ < Cu2+ < Zn2+
– This trend is referred to as the Irving Williams
order
– Note smaller ions in general bind a given ligand
more effectively. You would expect this as the
smaller ions are expected to be stronger Lewis
acids other things being equal

Chelate effect
‹ The equilibrium constants for chelate
complexes are usually larger than for similar
non-chelate complexes
– Ni(OH2)62+ + 6NH3 = Ni(NH3)62+ + 6H2O K1
– Ni(OH2)62+ + 3en = Ni(en)32+ + 6H2O K2
– K2 > K1
‹ The effect is mainly due to entropic differences
between the two reactions

42
 Thermodynamics and the chelate effect
‹ Experiments comparing the thermodynamics of complex
formation suggest that the reason chelate complexes are
more stable than similar complexes formed with
monodentate ligands is entropic
NH3 complexes en complexes Chelate effect

∆G ∆H ∆S ∆G ∆H ∆S ∆∆G ∆∆H ∆∆S

[Ni(NH3)2(H2O)4 ]2+ -29.0 -33 -12 [Ni(en)(H2O)4]2+ -41.9 -38 17 -12.9 -5 29
[Ni(NH3)4(H2O)2]2+ -46.3 -65 -63 [Ni(en)2(H2O)2]2+ -77.2 -77 12 -30.9 -11 74

[Ni(NH3)6]2+ -74.2 -92 -58 [Ni(en)3]2+ -111.8 -107 29 -50.0 -17 121

∆G, ∆H and ∆S are for reactions involving replacement of water by ammines. ∆∆G,
∆∆H and ∆∆S is the difference between the values for the ammonia and en complexes

Rates of reaction
‹ Reactions involving transition metal complexes do not
all occur at the same rate. Many reactions are very fast,
but some are incredibly slow
– Complexes that undergo ligand replacement rapidly are said to
be labile
– Complexes that undergo ligand replacement very slowly are
said to be inert
‹ The reactivity of a complex in a ligand substitution
reaction can be rationalized by considering a
combination of charge/size ratio for the cation and the
LFSE of the starting complex

43
Water exchange rates
‹ The exchange of water between the bulk solvent and the
coordination sphere of the aquo complex of a metal ion is a reaction
with no enthalpy change. The determination of its rate provides a
useful guide to the lability or inertness of complexes involving
different metal ions
– [M(OH2)n]m+ + H2O* == [M(*OH2)(OH2)n-1]m+ + H2O
» The rate of this reaction can be followed by using isotopically labelled bulk water
and monitoring how fast the isotope is incorporates into the complex

High charge and small size

favor slow ligand exchange.
Metals showing high LFSE
in their aquo complexes also
show slow exchange

Reaction mechanisms
‹ Balanced chemical equations are typically
written to communicate what the reactants and
products are. However, in order to understand
why you get certain products and why a reaction
occurs at a given rate it is sometimes necessary
to understand how the reaction occurs
‹ A description of how a reaction occurs is
referred to as a reaction mechanism

44
Mechanism of substitution reactions
‹ Ligand substitution reactions in transition metal complexes are
examples of nucleophilic substitutions
– This a very common type of reaction in inorganic, organic and
biochemistry. The nucleophile is an electron donor (Lewis base) that
attacks (forms a bond with) an electron deficient site in a molecule.
‹ There are two extreme possibilities describing how the
substitution occurs
– We could imagine the nucleophile forming a bond with the atom that it is
attacking before the group that it is ultimately going to replace has
started to leave, and then the leaving group leaves. This mechanism
would be described as associative and it is often referred to as an SN2
reaction (substitution nucleophilic bimolecular)
– Alternatively we could view the reaction as involving the loss of the
leaving group from the substrate. Followed later by the nucleophile
coming in and making a bond to the metal center. This would be
described as a dissociative reaction and denoted SN1

Associative reactions
‹ Many square planar Pt(II) species react via an
associative mechanism
– trans [PtClX(py)2] + Y--> trans [PtClY(py)2] + X
‹ It is observed that the rate of this type of reaction is
strongly dependent on the nucleophile (Y) and almost
independent of the leaving group (X)
– This strongly suggests that the rate limiting step in the
reaction involves the formation of a Pt-Y bond and that Pt-X
bond breaking is not part of the rate limiting step

Y
Pt X Pt Pt Y X
X
Y

45
 Dissociative reactions
‹ Substitution in many octahedral complexes go via a
dissociative mechanism
– Rates depend strongly on the leaving group and only
slightly on the nucleophile suggesting that the rate limiting
step involves breaking the metal leaving group bond

X Y
M M X M

Y
Intermediate has a lower
coordination number than the
reactant – hence dissociative

Oxidative addition and reductive elimination

‹ These reactions are important in the operation of many industrial
catalysts
‹ Oxidative addition is a reaction where the coordination number of
the metal increases at the same time as its formal oxidation state
increases
Ph3 P Cl Ph3 P H H
Ir H2 Ir
OC PPh3 OC PPh3
Cl
‹ Reductive elimination is a reaction where the coordination
number of the metal decreases at the same time as its formal
oxidation state decreases
RCO
Ph3P CH3 Ph3P Cl
Rh Rh RCOCH3
OC PPh3 OC PPh3
Cl

46