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Reaction Mechanism of d-metal complexes

Chapter 20

Inorganic Chem 160:371


November 2010
M. Greenblatt

Ligand substitution reactions: one Lewis base (Y) displaces another (X)
Y + M-X M-Y + X
e.g.,

[Co(OH2)6]2+ (aq) + Cl- (aq) [CoCl(OH2)5]+ (aq) + H2O (l)

Both thermodynamic and kinetic effects determine chemical reactionA reaction may be thermodynamically possible (G < 0), yet kinetically it is not
reactive (nonlabile)
Equilibrium, or Formation constants:
e.g., coordination equilibrium for ligand substitution is
[Fe(OH2)6]3+ (aq) + SCN- [FeSCN(OH2)5]2+ (aq) + H2O )l)
Kf = [FeSCN(OH2)52+] / [Fe(OH2)6 3+][SCN-]
Kf is the formation constant of the complex; if Kf is large, incoming L binds
Stronger than H2O (solvent); if Kf is small, H2O binds stronger than L

Kf spans a huge range, depending on M and L

If more than one L is replaced by substitution, then Kf is more complex:


[Ni(OH2)6]2+ (aq) + 6NH3 [Ni(NH3)6]2+ (aq) + 6H2O (l)
At least 6 steps are involved:
[Ni(OH2)6]2+ (aq) + NH3 (aq) [NiNH3(OH2)5]2+ (aq) + H2O (l)
Kf1 =
[NiNH3(OH2)5]2+ (aq) + NH3 (aq) [Ni(NH3)2(OH2)5]2+ (aq) + H2O (l)
Kf2
etc..to Kf6
in general
Kf1 > Kf2>Kf3>Kf6..
This is understood in terms of G0 = -RTlnKf successive Kf decrease due to
decreased # of H2O available for replacement - deminishing statistical factor
is reflected in stepwise Kf values for for above reaction

Note Kfn/Kfn+1 is not very large

In general:
M + L ML

Kf1 = [ML]/[M][L]

ML + L ML2

Kf2 = [ML2/[ML][L]

MLn-1 + L MLn

Kfn = [MLn/[MLn-1][L]

Overall formation constant:


M + nL MLn

n = [MLn]/[M][L]n

n = Kf1x Kf2..Kfn
What are the dissociation constants of MLn?
ML M + L etc

A reversal of this trend indicates an electronic, or structural change


e.g.: Kfn > Kfn+1
[Fe(bipy)3] 3+ much more stable than [Fe(OH2)2(bipy)2]3+
LFSE of LS, t2g5eg0 >> LFSE of HS t2g3eg2
[Fe(OH2)6]3+ (aq) + bipy (aq) [Fe(OH2)4(bipy)]3+ (aq) + 2H2O (l)
log Kf = 4.2
[Fe(OH2)4(bipy)]3+ (aq) + bipy (aq) [Fe(OH2)2(bipy)2]3+ (aq) + 2H2O (l)
log Kf = 3.7
[Fe(OH2)2(bipy)2]3+ (aq) + bipy (aq) [Fe(bipy)3]3+ (aq) + 2H2O (l)
log Kf = 9.3

Also if Kfn+1 < Kfn some change has occurred


Note the reaction of [Hg(OH2)6]2+ + ClKf1 = 6.74; Kf2 = 6.48; Kf3 = 0.85
[HgCl2(OH2)4] (aq) + Cl- (aq) [HgCl3(OH2)]- (aq) + 3H2O (l)
CN = 6 CN = 4

Chelate effect
1. [Cd(OH2)6 ]2+ (aq) + en (aq) [Cd(en)(OH2)4 ]2+ (aq) + 2H2O (l)
2. [Cd(OH2)6 ]2+ (aq) + 2NH3 (aq) [Cd(NH3)2(OH2)4 ]2+ + 2H2O (l)
H are similar, S(1) = +13 J(Kmol)-1, S(2) = -5.2 J(Kmol)-1
Chelate complexes are always more stable due to increase of S & kinetic effect

G H-TS
chelate effect has important applications: porphyrin, edta4- complexing agents,
biochemical metal sites
very large Kf (1012-1025 indicates chelated complex

Examples of chelate comlexes

Diamine metal comlex

Note five membered


rings-stable

Photon driven oxidation system


to generate O2 from H2O with Solar energy
-MnO2 Catalyst

eRuII*(bpy)3

O2 + 4H+

S2O82-

2H2O
SO4- + SO42-

RuII(bpy)3/RuIII(bpy)3
Eox = 1.4 V

e-

Illumination was done using 250W industrial light source with UV filtered by Pyrex
and IR with a 12 cm path water filter at intensity of 20 mWcm-2.

Irving-William Series: summarizes relative stabilities of M2+ complexes


and reflects electrostatic and LSE effects
Ba2+<Sr2+<Ca2+<Mg2+<Mn2+<Fe2+<Co2+<Ni2+<Cu2+>Zn2+

Note sharp increase in Kf for


Fe2+, d6, to Cu2+ d9 LSE
decrease for Zn2+, d10 (LSE=0)
Why Kf (Cu2+ complex) > Kf (Ni2+ complex)?

Ligand substitution reactions


MLxX + Y MLxY + X
X is the leaving group and Y is the entering group
Kinetically complexes are inert and labile
Metal complexes that react with t1/2 1 min are kinetically labile
If the reaction is significantly longer than this, it is considered kinetically nonlabile, or
inert
No relationship between thermodynamic stability and lability towards substitution.
e.g., hydG of Cr3+ and Fe3+ are similar,
[Cr(H2O)6]3+ d3 undergoes substitution slowly, while Fe(H2O)6]3+ d5 fast
Overall formation constant of [Hg(CN)4]2- is greater than that of [Fe(CN)6]4Hg(II) complex is kinetically labile and exchanges CN rapidly (with isotopically
labelled CN, while Fe(II) d6 HS slowly; d3 and d6 complexes are extra stable
due to LFSE

Average residence time, = 1/k of H2O in first coordination sphere of a metal ion
Note huge range for d-metals: function of dn
e.g., [Cr(H2O)6]3+ d3, [Rh(H2O)6]3+ LS d6 LFSE
k
[M(OH2)x]n+ + H2O

[M(OH2)x-1 (OH2)]n+ + H2O

rapid

Rate of H2O exchange = xk[M(OH2)xn+]


[Ir(H2O)6]3+ slow, = 109
= 290 years

Lanthanides are large ions, k > 107

Main group
k for H2O exchange
Increases with:
increasing size of M
increasing coordination #
decreasing surface charge density (Z/reff)

Some generalizations about reactivity:


1.Metal comlexes without extra stability (e.g., LFSE & chelating L, are labile)
2.Very small ions are less labile, because of strong M-L bond and steric
effects
(difficult for Y to approach M)
3. All complexes of s (except Be2+ and Mg) are labile)
4. Complexes of M(III) f-block are all very labile
5. Complexes of d10 ions (Zn2+, Cd2+, Hg2+) are normally labile
6. Across d series M2+ are generally labile with distorted Cu2+ most labile
7. Across d series M3+ are distinctly less labile than M2+
8. d-M comlexes with electronic configurations with d3 and d6 (Cr(III), Co(III)
are nonlabile due to large LFSE, chelate complexes, like [Fe(dipy)]2+ are even
more nonlabile
9. 4d, 5d metal complexes are usually nonlabile, because of large LFSE (LS)

1. Identities of Ls effect rates of reaction; incoming L has greatest effect on rate


2. Keq of displacement reaction can rank Ls in order of their strength as Lewis bases
3. For kinetics, concept of nuclephilicity is used (instead of equilibrium concept of basicit
4. Nuclephilicity: rate of attack on a complex by a Lewis base elative to the rate
o attack by a reference Lewis base

Mechanism of reactions sequence of elementary steps by which the reaction takes place
often not all the steps can be determined, only the slowest step, the rate determining step
First step in elucidating mechanism is determination of the
rate law - how rate changes with concentration of reactants
e.g., [Ni(OH2)6]2+ (aq) + NH3 (aq) [Ni(OH2)5]2+ (aq) + H2O
Rate = k[Ni(OH2)62+][NH3]
Generally the slowest elementary step of reaction controls the overall rate
of raction and the overall rate law this is the rate-determining step

Mechanism is usually proposed: it must be consistent with all the experimental


facts. A mechanism often cannot be proven, since another mechanism may also
be
consistent with the experimental data.
For substitution reactions, square planar and octahedral complexes
will be considered only

Stoichiometric equations often say nothing about mechanism


[(H3N)5Co(CO3)]+ + 2H3O+ [(H3N)5Co(H2O)]3+ + CO2 + 2H2O
This might suggest direct substitution of CO32- by H2O
However, use of H218O solvent shows that all the O in the [(H3N)5Co(H2O)]3+
complex comes from CO32-

2+

Proposed mechanism:

H
+ H2O

[(H3N)5Co(OCO2)] + H3O+ [(H3N)5Co O


CO2

[(H3N)5Co(OH)]2+ + CO2 + H2O


H3O+
[(H3N)5Co(H2O)]3+ + H2O

Classification of mechanisms for nucleophilic substitutions


dissociative, associative and interchange

Dissociative (D):
MLxX {MLx } + X
intermediate

leaving group

{MLx } + Y MLxY
entering group

Typical profile of a reaction with D mechanism


e.g., W(CO)6 W(CO)5 + CO
W(CO)5 + PPh3 W(CO)5Ph3
The intermediate W(CO)6 has been isolated

Associative:
MLxX + Y {MLxXY}
entering group

{MLxXY} MLxY + X
intermediate

leaving group

This mechanism in square planar


Complexes of d8 M (Ni(II), Pd(II), Pt(II), Ir(I)
e.g., [Ni(CN)4]2- + 14CN- [Ni(CN)4 14CN]3[Ni(CN)4(14CN)]3- [Ni(CN)3(14CN)]2- + CNIntermediate
was isolated

Interchange (I) mechanism


MLxX +Y YMLxX MLxY + X
Transition state
In most substitution pathways: bond formation with Y and bond
breaking with X is concurrent. In the I (interchange) mechanism: no
intermediate phase but various transition states:
Difference between A and I is
life time of intermediate state
if it is long enough, and can be detected, A

e.g., [Ni(CN)5]3- trigonal bipyramid was observed


experimentally and isolated in the
solid state intermediate in square planar
substitution reaction
trans and cis transformation also evidence for
trigonal bipyramidal intermediate

MLxX +Y YMLxX MLxY + X


Transition state

n most substitution pathways: bond formation with Y and bond breaking


with X is concurrent. In the I (interchange) mechanism: no intermediate
phase but various transition states:
dissociative interchange (Id) bond breaking dominates bond forming
associative interchange (Ia) bond formation dominates over bond
breaking
In associative (A) and Ia the reaction rate shows a dependence
on the entering group (Y);
in dissociative (D) and Id very small dependence on entering group.
In general it is difficult to distinguish between A and Ia and D and Id.
An interchange mechanism is a concerted process in which there is
no intermediate species with a coordination number different from
that of the starting complex

Rate determining step is Associative, if rate strongly depends on the incoming L


Typical of square planar substitution reaction of d8 metal complexes
[PtCl(dien)]- (aq) + I- (aq) [PtI(dien)]+ (aq) + Cl- (aq)
Rate with Br- increases rate by an order of magnitude

Profile of mechanisms
with associatively activated steps:

a. Associative mechanism associatively


activated, Aa - formation of MLnXY is rate
determining step

b. Dissociative mechanism, associatively


activated - Da formation of MLnY is rate
determining step

Profile of mechanisms
with dissociatively activated steps: rate is
largely independent on identity of Y
(substitution in octahedral comlexes)

Dissociative mechanism associatively


activated, Ad if loss of X in MLnXY is rate
determining step

b. Dissociative mechanism, dissociatively


activated - Dd if initial loss of X from MLnX
is rate determining step

Profile of Interchange mechanisms


Can be either associative or dissociative

a. Interchange mechanism associatively


activated, Ia if rate depends on formation of
M.Y bond

b. Interchange mechanism, dissociatively


activated - Id if rate depends on rate at
which MX bond breaks

Eyring Eq.- f (T, H#, S#)


k = (kT/h)e-G#/RT = kT/h)e [-H#/RT +S#/R]
Linearized form:
ln(k/T) = -H#/RT + ln(k/h) + S#/R
Pg 765 transition state

k = rate constant
H# =enthalpy of activation (J/mol)
S# = entropy of activation (J/mol-K)
k = Boltzman const
h= Plancks const.

From Eq: ln(k/T) = -H#/RT + ln(k/h) + S#/R


Plot of ln(k/T) vs 1/T (Eyring plot)

Large negative S# indicative associative

Pressure dependence of k V#
Volume of activation (cm3/mol)
d(lnk)/dP = -V#/RT
k = rate const.
P = pressure
V# =volume of activation (Vtran-Vinit)
R = molar gas const.
T = temperature (K)
integrated form:
Ln[(k(P1)/k(P2)] = (-V#/RT)(P1- P2)
negative value of V# associative
positive value of V# dissociative

Substitution in Square Planar complexes


d8 configuration, Rh(I), Ir(I), Pt(II), Pd(II), Au(III) form square
planar comlexes
Many kinetic studies on nucleophilic substitution of Pt(II) square planar
complexes indicate that the mechanism is associative or Ia :
S# and V# are negative

k for the substitution of Cl- by H2O in [PtCl4]2-, [PtCl3(NH3)]-,


[PtCl2(NH3)2], and [PtCl(NH3)3]+ are similar,
suggests an associative mechanism

Substitution in a Pt(II) square palanar complex:


PtL3X + Y PtL3Y + X
Experimental rate law:
Rate = -d[PtL3X]/dt = k1[PtL3X] + k2[PtL3X][Y]
suggests that reaction proceeds simultaneously by two routes:

If reaction is studied under psuedo-first order conditions, S=olvent


Y and S are in large excess: [Y]t ~ [Y]0; [S]t ~ [S]0

Rate= -d(PtL3X)/dt = kobs[PtL3X]; kobs = k1 +k2[Y]

Rate = -d(PtL3X)/dt = k1[PtL3X] + k2[PtL3X][Y]


Rate= -d(PtL3X)/dt = kobs[PtL3X]
kobs = k1 +k2[Y]

k2 from associative
mechanism is effected by Y

Study k vs [Y] (Y in large excess; conc. ~const.)

Here solvent for both is CH3OH


With different solvent, k1 intercept, differen

Effect of solvent on k1: in polar solvents k1 dominates; in apolar S


contribution of k1 is diminished, hence S participates in reaction, so

Rate = -d(PtL3X)/dt = k3[PtL3X][S] + k2[PtL3X][Y]


k1 =k3[S]

Nucleophilicity of Y
f
for a specific
complex is given by
the nucleophilicity parameter
nPt = log k2[Y]/k20
k2[Y] is the second-order rate const
for
trans-[PtCl2(py)2] + Y [PtYCl(py)2]- + ClAnd k20 is the rate const when Y is CH3OH
Note: if nPt is large, Y is highly nucleophilic
nPt seems to correlate with softness of base
Cl- < I-; NH3 < P

Rate = -d(PtL3X)/dt = k1[PtL3X] + k2[PtL3X][Y]

(25.9)

k2 arises from associative mechanism, attack of Y on PtL3X, and is dominant when


Y is a good nucleophile;
but k1 term, which may indicate a concurrent dissociative pathway; in polar solvents k1
becomes dominant, its contribution diminishing in non-polar solvents
Thus solvent participates, and rate eq. (25.9) is better written as:
Rate = -d(PtL3X)/dt = k3[PtL3X][S] + k2[PtL3X][Y]
Since S is in excess, [S] = constant, and k1 = k3[S]
When S is a potential L like H2O, it competes with Y entering group in the rate determining
step, and X is displaced by either Y or S:
k2
PtL3X + Y PtL3Y + X
competes with:
k1
PtL3X + S PtL3S + X
fast
PtL3S + Y PtL3Y + X

this is non-rate determining

Further evidence that both k1 and k2 terms are associative in square planar substitution
reactions, is that as bulkiness of Y or S (L) increases, both rate constants decrease

Substitution at square planar complexes is stereo-retentiveentering group takes the coordination site of the leaving group

Trigonal bipyramid intermediate

Further evidence for trigonal bipyramid intermediate

The trans effect: the choice of the leaving group in a square planar complex
is determined by the nature of the ligand trans to it, and is kinetic in origin

NH3

Cl
{Cl

NH3

3
Pt Cl }2- {Cl Pt Cl}- NH

NH 3

Cl

{Cl Pt NH3}
Cl

Cl
NH3

{NH3Pt NH3}2+ Cl

NH3

cis
Cl

Cl

{NH3 Pt NH3]+ Cl
{NH3 Pt NH3}

NH3

Cl
trans

Preparation of cis- and trans-[PtCl2(NH3)2] by different routes, illustrates the


Trans effect

One contributing factor to the trans effect is the


trans - influence (Box 23.9)

L and L compete for electron density-use same metal


orbitals (dz2 and pz) for M-L and ML bonds
L
|
XMX
|
L
Cl
|
ClPtCl
|
Cl
Pt-Cl (pm)

231.6

}2-

The existence of ground-state trans influence (the effec


of L on M-L bond) is established by solid state structure,
vibration (IR) and NMR data for a series of related
complexes
H- exerts
H2C = CH2 } _

ClPtCl
b | a
Cl

PMe3

|
Cl PtPMe3
|
Cl

a=232.7; b=230.5

2041
-7.8

2156
-12.7

2178
-15.6

|
Cl Pt H
|
Cl

a = 237

IR and 1H NMR data for trans-[PtXH(PEt3)2]


XCNIBr(Pt-H)cm-1
(1H for Pt-H)

Strong trans-influence
PEtPh2

a= 242

Pt-H bond is weakest for


X=CN- trans-influence of X-:

Cl- E = h (IR; 1/)

CN- > I- > Br- >Cl2183 higher H, lower

-16.8gH = h

The trans - influence is not the same as the trans effect


The former is a ground state phenomenon - structural trans-effect
the latter is a kinetic effect kinetic trans-effect

The second factor, responsible for the kinetic origin of the trans - effect is
bonding in the 5-coordinate transition state, or intermediate as shown:

L2 and M can only communicate electronically via -bonding


if they all lie in the same plane in the transition state.
This implies that the transition state must be
trigonal bipyramidal, rather than square pyramidal

If L2 is a strong -acceptor, such as CO, CN- or H2C=CH2


it will stabilize the transition state by accepting electron density that the
incoming nucleophilic ligand (Y) donates to M and thereby facilitate
substitution at the site trans to it

General order of the trans - effect: the general ability of


ligands to direct trans substitution spans a factor of ~106 in
rates and is:

H2O OH- NH3 py < Cl- < Br- < I- [NO2 ]- <
Ph- < Me- < PR3 H- << CO [CN]- C2H4
Trans-effect is useful in synthesis of Pt(II) cis
or trans complexes (see 26.19, 26.20)

Ligand Nucleophilicity
Substitution in Pt(II) complexes depends on
nucleophilicity of Y
the rate constant k2 (Eq. 26.12)
Rate = -d[PtL3X]/dt = k1[PtL3X] + k2[PtL3X][Y] (26.12)
increases in the order of the nucleopholicity sequence:

H2O < NH3 ~ Cl- < py < Br- < I- < CN- < PR3
Nucleophilicity parameter
nPt = log k2/k2 or nPt = logk2 logk2
k2 is the rate constant for:
trans-[PtCl2(py)2] + CH3OH trans-[PtCl(py)2CH3OH]+ + ClnPt = = for Y = CH3OH

The nucleophilicty parameter, nPt describes the dependence of the rate of substitution
in a square planar Pt(II) complex on the nucleophilicy of the entering group, Y

trans-[PtCl2(py)2] + CH3OH trans-[PtCl(py)2CH3OH]+ + Cl- 26.21

A linear relation of log k2 vs nPt for Pt(II) square planar comlexes


of Y is observed for the generally, reaction:
PtL3X + Y PTL3Y + X
Equation of the straight
line is defined by:
log k2 = s(nPt) + logk2
s = nucleophilicity
discrimination factor
logk2 = rate when
Y = CH3OH

Ligand substitution in Octahedral complexes


H2O exchange in [M(H2O)6]n+ complexes
[M(H2O)6n+ + H2(17O) [M(H2O)5{H2(17O)}]n+ + H2O
with M an s, p or d metal, this reaction can be studied with 17O NMR

First order rate constants for the above exchange show the following trends

1. For s and p metals k increases with increasing ionic radius, r+


2. For similar r+ (Li+, Mg2+, Ga3+) increase of charge, slows down reaction

3. For M2+ d-metals, no correlation of k with r+, but there is with


dn
4. Limited data for M3+ d ions support behavior as in 3

associative
dissociative

associative

Suggests that bond breaking becomes less (and bond making


more) important for d3 to-d5 configuration

For first row d-Mn+ ions (all HS) k for H2O exchange varies greatly:
Cr2+ d4 and Cu2+ d9 are kinetically very labile (k 108 s-1)
Cr3+ d3 is kinetically inert (k 10-6 s-1)
V 2+ d2 k 102 s-1, less labile than later M2+ ions.
The rates of water exchange in HS hexa-aquao complexes follows the sequence:
V2+ < Ni2+ < Co2+ < Fe2+ < Mn2+ < Zn2+ < Cr2+ < Cu2+
and
Cr3+< V3+ < Fe3+ < Ti3+
For a series of ions of similar charge, size, undergoing the same reaction of the
same mechanism, it can be reasonably assumed that the collision frequencies and
S# are approx. constant and the variation in rate is attributed to H# ,
which is dependent on loss or gain of LFSE.

Model for change of LFSE in going to 5- (dissociative)


or 7- (associative) coordinated complex
loss of LFSE means increase in H# and slower k

V2+ < Ni2+ < Co2+ < Fe2+ < Mn2+ < Zn2+ < Cr2+ < Cu2+

Despite the qualitative nature of CFT/LFSE, good agreement between labality


and LFSEs for example for either model, Cr2+ and Cu2+ are most labile due JT

The Eigen - Wilkinson Mechanism of ligand substitution


in an octahedral complex
Water exchange is always more rapid than substitution with other ligands:
ML6 +Y products
For most ligand substitutions in octahedral complexes, experimental evidence
supports dissociative mechanism; two limiting cases are observed:
at high conc of Y, rate is independent of [Y], pointing to disociative mechanism
at low conc of Y, the rate depends on [Y] and [ML6], indicative
of associative mechanism
These apparent contradictions are explained by The Eigen - Wilkinson Mechanism:

An encounter complex is formed between the substrate and entering ligand


in a pre-equilibrium step, followed by loss of a leaving ligand in a
rate-determining step

Eigen-Wikinson mechanism
[Ni(OH2)6]2+ + NH3 [Ni(OH2)5 (NH3)]2+ + H2O
1st step diffusion of reactants to form a pre-equilibrium pair
[Ni(OH2)6]2+ + NH3 {[Ni(OH2)6]2+, NH3}

~1 ns

and in general:
KE
ML6 +Y {ML6,Y}
Encounter complex
KE = {ML6,Y}/ [ML6][Y]
KE can be rarely determined experimentally,
sometimes can be calculated/estimated theoretically

2nd step is the rate determining step in the Eigen - Wilkinson


Mechanism
{[Ni(OH2)6]2+, NH3} [Ni(OH2)5(NH3)]2+ + H2O
in general
k
{ML6 ,Y} ML5Y + L
Rate = k[{ML6,Y}]
Cannot just use from
KE = {ML6,Y}/ [ML6][Y]
[{ML6,Y}] = KE [ML6][Y] as [ML6] is less by the amount that is in the
encounter pair

Rate = k [{ML6,Y}]
[{ML6,Y}] cannot be measured directly, but KE can be estimated
KE = [{ML6,Y}] / [ML6] [Y]
[M]total is the total concentration of the complex
[M]total = [ML6] + [{ML6,Y}]
[M]total = [ML6] + KE [ML6] [Y]
= [ML6] (1+KE[Y])
[ML6] = [M]total / (1+KE[Y])
thus substituting in the rate expression above
[{ML6,Y}] =KE[ML6][Y]

Rate = k KE [M]total [Y] / (1+KE [Y])

Rate = k KE [M]total[Y] / (1+KE[Y])


at low conc. [Y] << 1, K[Y] << 1

Rate = k KE [M]total[Y] = kobs [M]total[Y]


kobs = kKE kobs is measured experimentally, KE can be measued, or
is estimated by theory
so

k = kobs/KE

Rate = k KE [M]total [Y] / (1+KE [Y])


At high conc. of Y, e. g., when Y is the solvent (e.g., H2O
exchange)

KE[Y]) >> 1
Rate = k [M]total (first order rate eq.)
kobs = k
Thus reaction with solvent can be compared with other Y, without
needing to know KE

Further exp. evidence that ligand substitution in octahedral complexes is D


or Id is supported by many examples:
The rate of ligand substitution depends on the nature of the ligand leaving
[Co(NH3)5X]2+ + H2O [Co(NH3)5H2O]3+ + XFor above reaction, rate of substitution increases as:
OH- < NH3 NCS- < MeCO2- < Cl- < Br- < I- < NO3-

Rate constant, k for the substitution reaction:


R
a
t
e
c
o
n
s
t
n
t
s

[Ni(H2O)6]2+ + Y [Ni(H2O)5Y]2+ + H2O

The fact that k varies so little is consistent with a Id mechanism


if the path was associative, k would depend on nature of Y more

f The substitution of an uncharged ligand (H2O) by an anionic one (F-)


o
is called anation
r
t

OH- < NH3 NCS- < MeCO2- < Cl- < Br- < I- < NO3-

This trend correlates with M-X bond strength; the stronger the bond,
lower the rate and consistent with dissociative mechanism
with bond breaking the rate-determining step

Leaving group effect -the identity of X has large effect on dissociatively


activated reaction rate depends on M.X : lnk = lnK + c; plot of lnk vs
lnK
2+
3+
[Co(NH3)5X]

+ H2O [Co(NH3)5H2O]

+X

k is rate const for forward react., K is equilibrium const

G# -log k LFER with a slope < 1 has associative character


G0 -log K as indicated for analogous Rh(III) complexes
G# = pG0 + c For Co(III) rate goes as I- > Br- > Cl- for
P 1, i.e.,
For Rh(III) rate is reversed I- < Br- < Clslope 1 Co(III) is hard, forms weaker bond with I- than Clslope = 1.0
Rh(III) is softer, forms weaker bond with Cl- than I-

this linear relationship between log k and log K represents


linear relationship between G# and G0 called
linear free energy relationship (LFER)

Effect of changing X to X on G# & pG0


G# = pG0 + c linear f(X) with
slope, p ~ 1
and shows that for D or Id
X has the same effect on the
formation of MX transition state
as it has on G0 for the
complete elimination of X-

Spectator ligands

effect the rate of substitution in octahedral complexes by the


strength M L interactions
trongest donor ligands increasing the rate, by stabilizing the transition state

In Co(III) and Cr(III) both cis and trans L effect rate of substitution in
proportion to strength of M-L bond, but no important trans effect
e.g., [NiXL5]+ + H2O [NiL5OH2] + H2O
Much faster with L = NH3 than L = H2O, because NH3 is better
donor, large electron density on M enhences M.X break more readily
also
larger electron density on M stabilizes reduced coordination
of transition state
Steric crowding favors dissociative activation
formation of transition state relieves crowding

Effect of Spectator Ligand

Stereochemistry of substitution-square-pyramidal intermediate leads


[CoX(en)2
+ H2O [Co(H2O)(en)2
both cis and trans were studied
A]+

A]2+

X-

retention of original geometry


trygonal-bipyramidal intermediate
can lead to isomerization

Table shows that


cis comlexes remain cis
trans comlexes undergo isomerization
to cis in order:
A = NO2- < Cl- < NCS- < OHThis can be understood in terms of Id for
the two different 5-coordinate
intermediate possible

Reaction through a square-pyramidal complex leads


to retention of geometry

Good -donor L(A) trans to


X, favor isomerization

Reaction through trigonal-bipyramidal complex


can lead to isomerization
cis octahedral complex leads to square-pyrmidal transition state
trans octahedral complex leads to trigonal-bipyramidal transition state
Good -donor L in equatorial position favor trigonal-bipyramidal

Electron -Transfer Processes


simplest involve only transfer of electrons and can be monitored by isotopic tracers

[56Fe3+(CN)6]3- + [59Fe2+(CN)6]4- [56Fe2+(CN)6]4- + [59Fe3+(CN)6]3two classes of electron transfer reactions were defined by Taube (Nobel Prize in
chemistry 1983)
in an outer sphere mechanism, electron transfer occurs without a covalent
linkage formed between the reactants
in an inner-sphere mechanism, electron transfer occurs via a
covalently bonded bridging ligand
Kinetic data can sometimes distinguish between these two cases, but
often, it is not possible to distinguish between inner- and outer-sphere
mechanism