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Chapter 20
Ligand substitution reactions: one Lewis base (Y) displaces another (X)
Y + M-X M-Y + X
e.g.,
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
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]
n = [MLn]/[M][L]n
n = Kf1x Kf2..Kfn
What are the dissociation constants of MLn?
ML M + L etc
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
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.
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
rapid
Main group
k for H2O exchange
Increases with:
increasing size of M
increasing coordination #
decreasing surface charge density (Z/reff)
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
2+
Proposed mechanism:
H
+ H2O
Dissociative (D):
MLxX {MLx } + X
intermediate
leaving group
{MLx } + Y MLxY
entering group
Associative:
MLxX + Y {MLxXY}
entering group
{MLxXY} MLxY + X
intermediate
leaving group
Profile of mechanisms
with associatively activated steps:
Profile of mechanisms
with dissociatively activated steps: rate is
largely independent on identity of Y
(substitution in octahedral comlexes)
k = rate constant
H# =enthalpy of activation (J/mol)
S# = entropy of activation (J/mol-K)
k = Boltzman const
h= Plancks const.
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
k2 from associative
mechanism is effected by Y
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
(25.9)
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
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
231.6
}2-
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
Strong trans-influence
PEtPh2
a= 242
-16.8gH = h
The second factor, responsible for the kinetic origin of the trans - effect is
bonding in the 5-coordinate transition state, or intermediate as shown:
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
First order rate constants for the above exchange show the following trends
associative
dissociative
associative
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.
V2+ < Ni2+ < Co2+ < Fe2+ < Mn2+ < Zn2+ < Cr2+ < Cu2+
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
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]
k = kobs/KE
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
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
+ H2O [Co(NH3)5H2O]
+X
Spectator ligands
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
A]2+
X-
[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