Inorganic reaction mechanisms

Substitution reactions
Thermodynamic factors
Kinetic factors
 Energy profile

Activated Complex
Ea, ΔH#, ΔS#

Kinetics
Y + M―X

Reactants Thermodynamics

M―Y + X
Products
 Thermodynamics
Both kinetics and thermodynamics are important in the assesment of a
reaction.
This is because some thermodynamically feasible reactions may be
kinetically hindered
Ligand substitution reactions will be used to illustrate these concepts:
Consider the reaction: Y + M ― X → M ― Y + X
This is a typical substitution reaction
Y = entering group
X = leaving group
The simplest illustration is a complex formation reaction:
e.g. [Co(H2O)6]2+ + Cl- → [CoCl(H2O)5]+ + H2O
 Aquo complexes
Fundamentally metal ions dissolved in water are complexed ÎAquo
complexes Î [M(H2O)x]n+

Formation of coordination compounds from an aqueous medium Î

requires displacement of aquo ligands by other ligands.

Î Several geometries are possible: Typical examples of aquo

compounds Î e.g. Co(II)

[Co(H2O)6]2+ [Co(H2O)4]2+
Octahedral Terahedral

In reality the value of x varies Î due to extensive hydrogen bonding

around the coordination sphere of M

Spectra and magnetic properties Î similar to hydrated salts of non-

coordinating anions Î Co(ClO4)2.6H2O; Co(NO3)2.6H2O
 Aquo complexes
Predominantly [Co(H2O)6]2+ Îoctahedral

Also general for the 1st transition series Î [M(H2O)x]n+; n=+2 or +3

Note: Cr(II); Mn(III) and Cu(II) show distortions in the octahedral

geometry due to Jahn-Teller effects

2nd and 3rd TS are much less certain Î octahedral probably Î higher
coordination also possible

Most M(H2O)6 exchange rapidly Î can easily be demonstrated by

isotopic labeling with 18O enriched H2O.

Aqua ions are more or less acidic Î dissociate as follows:

[M(H2O)x]n+ → [M(H2O)x-1(OH)]n-1 + H+
e.g. [Co(NH3)5(H2O)]3+ → [M(NH3)5(OH)]2+ + H+
 Formation constants
Formation constant: the strength of a ligand relative to the strength of
the solvent molecules (usually H2O) as a ligand.

[Fe(OH2)6]3+(aq) + SCN-(aq) [Fe(SCN)(OH2)5]2+(aq) + H2O(l)

In dilute solutions [H2O] Î constant; [Fe(SCN)(OH2)52+]

Kf
[Fe(OH2)6 3+][SCN-]

Step-wise formation constant: formation constant of each solvent

replacement stage.
Kf1 ; Kf2 ........Kfn
Overall formation constant: product of the step-wise formation
constants.
βn = Kf1Kf2........Kfn
 Successive formation constants
[ML]
M + L ML Kf1
[M][L]

[ML2 ]
ML + L ML2 Kf2
[ML][L]

[MLn]
MLn-1 + L MLn Kfn
[MLn-1][L]

[MLn]
M + nL MLn βn
[M][L]n
The inverse of each Kf is the
dissociation constant Kd Î:
[M][L] 1
M + L ML Kd1
[ML] Kf1
 Trends in successive formation constants
The general trend Î Kf1 > Kf2
…… Kfn-1 > Kfn. Formation constants of Ni(II)
ammines, [Ni(NH ) (H O) ]2+
This trend is a result of the 3 n 2 6-n

sequential decrease in number of n Kf Kn/Kn-1 Kn/Kn-1

H2O to be replaced. Exp Stat
Situations do arise where Kfn > Kfn-1 1 525
Generally there are 2 reasons to
2 148 0.28 0.42
account for anomalies in the
trends of successive Kf values: 3 45.7 0.31 0.53
1 Î due to a major change in 4 13.2 0.29 0.56
electronic structure of the
complex, e.g. moving from a high 5 4.7 0.35 0.53
spin (due to weak field H2O) to a 6 1.1 0.20 0.42
low spin complex.
2 Î due to a major structural change e.g. from an octahedral to a
tetrahedral or square planar geometry Î characteristic of some
halo complexes
Q. Consider the formation constants of the following Fe(II)
complexes: Justify the observed trend?

[Fe(bipy)(H2O)4]2+: Kf1: 4.2

[Fe(bipy)2(H2O)2]2+: Kf2: 3.7
[Fe(bipy)3]2+: Kf3: 9.3

Kf3: [Fe(bipy)3]2+ >> Kf2: [Fe(bipy)2(H2O)2]2+:

The reason is due to a major electronic shift Î

from a high spin (due to weak field H2O) t2g4eg2 (LFSE Δo = 0.4)
config Î

to a low spin t2g6 config (LFSE Δo = 2.4). Large increase Δo.

Therefore [Fe(bipy)3]2+ is more stable than [Fe(bipy)2(H2O)2]2+

Q. Justify the following observation in the successive formation
constants for complexes of cadmium with Br-:
[Cd(Br)(H2O)5]+: Kf1: 36.3
[Cd(Br)2(H2O)4]: Kf2: 3.47
[Cd(Br)3(H2O)3]-: Kf3: 1.15
[Cd(Br)4]2-: Kf4: 2.34
The anomaly here is that Kf4: > Kf3:

The reason may not be electronic since both H2O and Br- are
considered weak field ligands Î

The reason is due to a major structural shift from an octahedral

[Cd(Br)3(H2O)3]- configuration Î

to a tetrahedral [Cd(Br)4]2- geometry with the simultaneous

expulsion of 3 molecules of water from a restricted geometry

Most halo complexes of M2+ have tetrahedral or square geometry

 Irving-Williams series 10

The Irving-Williams series summarises the relative 8

stabilities of complexes formed by M2+ ions.
The series reflect a combination of electrostatic 6

log Kf
effects and LFSE.
For the series Ba2+ < Sr2+ < Ca2+ < Mg2+ the 4
observed trend is purely electrostatic.
For the TMs in addition to electrostatic effects , the 2
high values of Kf is due to additional stability from
0
LFSE. Ba Sr Ca Mg Mn Fe Co Ni Cu Zn

In terms of ionic radii Î RECALL: Δo is

Mn2+ > Fe2+ > Co2+ > Ni2+ > Cu2+ > Zn2+. highest at d3 and d8
But,
Generally for strong field ligands the observed order is:
Mn2+ < Fe2+ < Co2+ < Ni2+ < Cu2+ > Zn2+.
The additional stability of d9 Cu(II) is due to the influence of Jahn-
Teller distortion Î results in the strong binding of the 4 planar ligands
in tetragonally distorted Cu(II) complexes Î higher Kf values.
 Other thermodynamic factors
In addition to the foregone discussion the following thermodynamic
factors are also important to the stability of TM complexes:

The chelate effect: this is largely an entropy effect Î represents the

greater stability of a complex containing a chelated polydentate ligand
compared with the equivalent complex with an analogous monodentate
ligands. H O
H2O 2 OH2
N
N
N
Ru Ru
N N
N H2O OH2
H2O

Steric Effect: The size of ligands are important in determining the most
stable configuration Î e.g. octahedral vs. tetrahedral

Electron delocalisation: This is important in complexes containing

chelated ring structures. The empty ring π* orbitals act as electron sinks
that drain electrons from the full metal t2g non-bonding orbitals.
 Labile and non-labile complexes
The rate at which one complex inter-converts into another is determined
by the height of the activation barrier between the two:

Labile complexes: A complex with a half life of the order of

milliseconds; e.g. [Ni(H2O)6]2+ is said to be labile

Non-labile or inert complex has half-life of the order of minutes; e.g

[Co(HH3)5(H2O)]3+

Factors affecting lability of complexes:

Complexes with no stabilising LFSE or chelate effects are very labile
Complexes of small metal ions are less labile due to greater M-L bonds
Complexes of M(III) ions are less labile than those of M(II) ions
Complexes of d3 and low spin d6 config are non-labile Î high LFSE
Chelate complexes of metal ions with high LFSE (e.g. [Fe(phen)3]2+) are
very stable
Complexes of d10 ions (zero LFSE: Zn2+, Cd2+, Hg2+) are generally labile
Classification of
mechanisms

Associative (A);

Dissociative (D);

Interchange (Ia or Id)

 Classification of mechanisms
Dissociative: Interchange Associative:
5-coordinate intermediate 7-coordinate intermediate
D Id or Ia A
MLnX + Y MLnY + X
MLn+ X + Y MLnXY

MLnY+X
MLnX + Y MLnY+X MLnX + Y

Energy profile for Dissociative Energy profile for Associative

mechanism: Intermediate has lower mechanism: Intermediate has higher
coordination number than reactant. coordination number than reactant.
 Classification of mechanisms

No intermediate With intermediate

Intermediate Î occurs at a local E minimum Î may be isolated

Transition state occurs at an E maximum Î cannot be isolated
 Interchange I
In most TM substitution reactions Î bond formation between M + Y
happens concurrently with bond cleavage between M + X Î
Interchange mechanism:
MLnX + Y Y……MLn…….X MLnY + X

For an interchange mechanism Î there is no intermediate formed,

but various TS may be possible:

Hence there are 2 types of I:

‰ Dissociative Id: bond breakage dominates over formation and
‰Associative Ia: bond formation dominates over breakage

‰ It is often difficult to distinguish between:

‰ A and Ia
‰ D and Id
‰ Ia and Id
Substitution reactions
in square planar
complexes

‰ Referring to complexes of d8 ion TM

‰ Under a large crystal field:

Rh(I) Ir(I) Pt(II) Pd(II) Au(III)

 Steric Effects
Remember 4-coord. Ni(II) can be tetrahedral or sq planar (why?)

Nucleophilic subst. in sq. planar complexes Î usually A or Ia Î

the rate of the reaction is dependent on the nature of the entering
group Y

But steric crowding at the reaction centre by bulky groupsÎ

usually inhibits A or Ia reactions Î results in D or Id mechanism

k values for cis-[PtClL(PEt3)2] + H2O → cis-[Pt(H2O)L(PEt3)2]

Me
L= pyridine 2-Mepy 2,6-diMepy
PEt3
M PEt3
k/s-1 8x 10-2 2x 10-4 1x 10-6
Cl

The rate ↓ with ↑ in steric bulk around N→M bond

Î The Me groups hinder the attack by H2O
 Stereochemistry
Substitution reactions at square complexes are stereospecific Î the
original geometry of the complex is preserved:

‰ cis reactants lead to cis products

‰ trans reactants lead to trans products

‰ most of these are 16 electron complexes Î useful in catalysis

Î oxidative addition-reductive elimination (16 e↔18 e) chemistry

X
trans reactant 5 coord TS via A mech trans product
 The kinetic trans-effect and thermodynamic trans-influence
Since the substitution reactions of sq. planar TM complexes are usually A
or Ia, what factors determine the nature of the TS and

Why a 5 coordinate (trigonal bipyramidal or square pyramidal) TS?

Which ligand leaves is determined by the ligand trans to it Î

trans influence Î trans effect

σ-donor ligands Î Ligands capable of contributing more electron

density to the shared orbital between itself and the trans ligand, thereby
weakening the bond to the leaving group Î trans influence

π-acceptor ligands Î drain away electrons in A or Ia substitution

reactions Î TS characterised by high electron density at the metal
center due to a 5-coordinate intermediate Î trans effect
 The kinetic trans-effect and thermodynamic trans-influence
trans influence and trans-effect are related Î weakening the
bond to the trans-ligand and increasing the rate of substitution,

Note: there is NO close correlation between the relative

magnitudes of the two phenomena

Why a 5 coordinate (trigonal bipyramidal or square pyramidal) TS?

L2
The leaving group (X), the entering
group (Y) and the trans ligand L3 all lie X
in the same plane. The TS is
stabilised if L3 is a good π acceptor L3 dxy
ligand such as CO. The three are able
to communicate electronically via L1 Y
the π-bonding orbitals. good π acceptor ligand e.g. CO
Remember the influence of π bonding
on the crystal field splitting Δ
The kinetic trans-effect and thermodynamic trans-influence
 The trans effect

The trans effect states that the bond holding a group trans to an
electronegative group is weakened. This trans group is the first to
be removed in a substitution reaction
Kinetic Studies to determine trans-effect of ligands

L k (s-1)
C2H4, CO too fast
P(OMe)3 10.3
PEt3 6.6
PPh3 3.1
Me2SO 0.0082
Et2S 0.0024
Me2S 0.0015
NH3 6.3x10-6
H2O 8.0x10-8
Trans-influence from x-ray crystallography
 Trans-influence from vibrational spectroscopy

L ν Pt-Cl L ν Pt-Cl L ν Pd-Cl

(cm-1) (cm-1) (cm-1)
CO 322 py 336 py 342
SMe2 310 SMe2 336 Cl 330
C2H4 309 COD 327 NH3 327
SEt2 307 SEt2 324 EtSCH2CH2SEt 323
PPh3 279 NH3 321 H2NCH2CH2NH2 307
PEt3 271 PPh3 305 PCH3 297
PEt3 294
❑ Ligands with high trans-influence have high trans-effect.
❑ Exceptions to this rule include CO, C2H4, and DMSO.
❑ Frequency order for Rh(III)-Cl: H- >PR3 >Me- >CO >I- >Br- >Cl-.
❑ For octahedral complexes, trans-influence parallels trans-effect.
 Trans effect vs. trans influence

❑ The trans effect is the influence of a ligand (L) on the rate of

substitution of the ligand trans to it (X). It is a kinetic effect (ground
and transition states)
H- = CH3- = CN- = C2H4 = CO >> PR3 = SR2 > NO2 = SCN- =
I-> Br-> Cl-> py > RNH2 = NH3 > OH- > H2O
❑ The trans influence is the extent to which a ligand (L) weakens the
bond that is trans to itself. It is a thermodynamic effect (ground state).
Apply primarily to the leaving group
R3Si- = R- = H- > PEt3 > PMe2Ph > PPh3 > P(OPh)3 = CN- >
SEt2> Et2NH > py > OSMe2 = C2H4 = CO > Cl-
❑ The trans effect is often the manifestation of the trans
influence although there are some ligands (DMSO, CO, C2H4) which
do not show significant trans-influences yet show strong effects
 Theory on trans influence

❑ Grinberg Polarization Theory (1935): M→ L and then L→ M induced

dipole results in repulsion of electrons in X Î weakening of M-X
bond.

❑ Chatt/Orgel theory of back-bonding: Stabilisation of a 5 coordinate

(trigonal bipyramidal) activated complex.

X
Q. Does back-bonding generally indicate stronger trans effect?

YES……….
……………and NO
Q. Given Pt(NH3)4]2+, [PtCl4]2-, HCl and NH3 suggest synthetic
routes to
a) cis-[PtCl2(NH3)2]
b) trans-[PtCl2(NH3)2]

H3N NH3 H3N Cl H3N Cl

HCl HCl
Pt Pt Pt
H3N NH3 H3N NH3 Cl NH3

Cl Cl Cl NH3 Cl NH3
NH3 NH3
Pt Pt Pt

Cl Cl Cl Cl Cl NH3