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Reaction Mechanisms of Inorganic Compounds

C21J, 4 Lectures
Mohammed Bakir, Office #8
 Introduction

 Ligand substitution reactions


 Octahedral Complexes
 Square Planar
 Racemization Reactions
 Reference: Chapters 9
 Textbook: B. Douglas, D. H. McDaniel, & J.
J. Alexander, Concepts & Models of
Inorganic Chemistry, 2nd edition, Wiley,
New York
Some Chemistry of Transition Metals
Ligand Exchange

Photochemical Coordination to metals

Redox Reactions Ligand Reactivity

Rearrangement of coordination
Sphere
What are reaction mechanisms?
 Detail step-by-step analysis of reaction
pathway.
 i.e. sequence of reactions involved in the
conversion of reactants to products
 Rate Law

 ‘Intimate’ Mechanism refers to details of


the mechanism at the molecular level.
Reaction Profile
Consider the reaction:
M + L W ML
MWL W [ML]* W [ML] W [ML]**
Collisions Activated Complex Intermediate Activated Complex
of >Energy Transition State

ML Width related to entropy


∆S
Narrow for –∆
Wide for + ∆S

Potential Energy
Potential Energy

Activation
[ML]* Energy α ∆G‡
[ML]* [ML]**

M+L M + L [ML]

ML ML

Reaction Coordinate
Reaction Coordinate
Microscopic Reversibility

 Microscopic reversibility: at equilibrium


both forward and reverse reactions
proceed at equal rates backward and
forward and along the reaction coordinate.
Transition State Theory
 Rate = k[L][M]
 k α K‡ α exp (-∆G‡/RT)
 k α exp (∆S‡/R) exp (-∆Εact/RT)

 Fast reactions are favored by:


 ∆S‡ more positive.
 ∆Eact less positive.
 Note since k is exponentially dependent on
∆S ‡ and ∆Eact. Small changes in k are not
significant in the interpretation of the rate
law.
Type of Reactions
 Ligand Substitution reactions: are those in which
the coordination sphere around the metal
changes due exchange of one ligand (lewis base)
with another ligand.

 e.g.
 Octahedral
ML6 + Y W ML5Y + L

[Cu(H2O)6]2+ + conc. HCl W[CuCl4]2- fast within


seconds

[Cr(H2O)6]3+ + conc. HCl W NO Reaction

 Square Planar
ML4 + YW ML3Y + L
Examples of Substitution Reactions

Cu2+ + H2O W [Cu(H2O)4]2+


Substitution reaction +NH3 -NH3

W
4H2O + [Cu(NH3)4]2+

[Cu(NH3)4]2++HCl+H2O → [Cu(NH3)3(H2O)]2+ + NH4+


H 2O
[Cu(H2O)4]2+
Fast reactions
+ Cl-

[Cu(H2O)3(Cl)]+
Example
 [Co(NH3)6]3+ + H2O → [Co(NH3)6(H2O)]3+
Slow several days

 Lability and inertness: kinetic terms &


unrelated to thermodynamic stability of
compound and they refer to how quickly a
reaction system reaches equilibrium.
 Inertness is kinetic stability
Examples
M(n-y)- + nCN- W [M(CN) ]
n
y

Kf = [M(CN)n]y/[Mn-y)[CN]n
 Compound Kf Exchange Rate

 [Ni(CN)4]2- 1030 very fast


 [Hg(CN)4]2- 1042 very fast
 [Fe(CN)6]3- 1044 very fast
 [Fe(CN)6]4- 1037 very fast
 [Pt(CN)4]2- ~1040 t1/2 = 1 min.

→ [Hg(CN)4]2- Thermodynamically stable but kinetically


labile, the same for [Ni(CN)4]2-
i.e. in solutions ligand exchange is fast but always with
CN-.
Thermodynamics versus Kinetics

 Thermodynamics → Stability
(stable/unstable)→ Kf Formation
Constant
 Kinetics →lability and inertness →rate
of replacement of ligands (bases)
Ligand Substitution Reactions in
Octahedral Compounds
 Kinetics of H2O exchange
LnM(H2O) + H2O*W LnM(H2O*) + H2O

(see Figure 1)
Kinetics of Water Exchange

Li+Na+K+ Rb+Cs+

Be2+ Mg2+ Ca2+Sr2+Ba2+

Al3+ Ln3+ Ln3+Zn2+ Cd2+ Hg2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Mn2+ Cu2+, Cr2+

100 102 104 106 108 1010

Exchange rate for metal aqua complexes


Figure 1
Langford & Gray Classes for Water
Exchange

 Class I Very fast (diffusion control), k >108 sec-1. The ions


in this class are those of alkali metals and alkaline earths
(except for Be2+ & Mg2+), Group IIB (except for Zn2+), Cr2+
and Cu2+.
 Class II Exchange-rate constants are between 104-108 sec-1.
The divalent first row transition metal ions (except for V2+, Cr2+
& Cu2+) as well as Mg2+ and the trivalent lanthanide ions.
 Class III Exchange-rate constants are between 1 and 104 sec-
1. This class includes Be2+, V2+, Al3+, Ga3+ and several trivalent
first-row transition metal ions.
 Class IV Exchange rate constants between 10-6 to 10-1 sec-1.
Member of the set are Cr3+, Co3+, Rh3+, Ir3+ and Pt2+. Inert.
Factors that affect water exchange
substitution reactions
 Ionic potential = q/r; charge & size of metal ions
 Ions with high ionic potential → slow reactions
suggesting that the main contribution to the activation
energy is the breaking of bond to the leaving group.
 d-electronic configuration
 →metal ions in strong LFSE → slow substitution
 Oh
eg
dx2-y2 dz2 6Dq

4Dq
t2g
dxy dxz dyz
Spectroelectrochemical Series
CN->phen~NO2>en>NH3~py>H2O>C2O42- >OH->F->S2-
>Cl->Br->I-

In strong field metal ions in d3, d4, d5, & d6 are inert
i.e. HIGH LFSE

Oh → high spin d8 such as NiII


& low spin d8 such as Rh(I), Ir(I), Ni(II), Pd(II), Pt(II) &
Square planar Au(III) are labil.
React faster than d6 & d3
For Cu2+ & Cr2+ the fast exchange is due to Jahn-Teller
distortion in the ground state which makes the axial bonds
longer than the equatorial bonds.
Mechanism of Ligand Substitution in Oh
Compounds
ML5X + Y → ML5Y + X
Where X is leaving group
Y is entering group
Wide ∆S +
Consider the following mechanism
k1

Potential Energy
ML5X Wk-1
k2
[ML5] + X ML5X

[ML5] + Y → ML5Y [ML ] ML Y 5 5

Dissociative pathway-D-type Reaction Coordinate


Key: M-X bond breakage, [ML5] is intermediate
Factors that affect the Strength
of M-X Bond
M -X Electrostatic
δ+ δ -
 Charge on metal Center-increase positive charge, M-X
bond strengthen
 Size of metal center-increase size of metal center, M-X
bond weaken
 Charge of leaving group, increase negative charge on X,
M-X bond strengthen.
 Size of leaving ligand, increase size of leaving group, M-
X bond weaken
 Charge on other ligands (spectator), increase negative
on other ligands, M-X bond weaken
 Size of spectator ligands, increase size of other ligands,
M-X bond weaken
Rate Law for Dissociative Mechanism

 Rate = d[L5MY]/dt =k2[L5M][Y]

Apply the steady-state approximation to L5M

 d[L5M]/dt = 0 =k1[L5MX] – k-1[L5M][X] –


k2[L5M][Y]

∴ [L5M] = k1[L5MX]/(k-1[X]+k2[Y])

& Rate = (k1k2[L5MX][Y])/(k-1[X] + k2[Y])


Bimolecular
Dissociative Mechanism, D-type
If k2[y]>>k-1[X]; i.e. pusedo 1st order

∴ Rate = k1[LnMX] unimolecular

e.g. aquation and anation of inert d6 CoIII


compounds of the type [Co(NH3)5X]2+.

For this mechanism [L5M] is an intermediate that


has an appreciable lifetime and can be
detected.

Note true examples of D-type are not common.


Aquation or acid hydrolysis
 Aquation or acid hydrolysis

L5MXn+ + H2O→ [L5M(H2O)]n+1 +X-


 Anation

[L5M(H2O)]n+1 + Y- →L5MYn+ + H2O


L5M-X → L5M—X → L5M….X

…..….
∆ +Y

Activation Energy Y
Vibrational Energy


-X
L5M-Y L5M…...X


Y

 The rate is insensitive to the identity of Y,


Implication is that both entering and leaving
groups are weakly bound in the transition
state. This is known as Dissociative interchange
(Id).
 No stable intermediate is observed
Plausible Mechanism for Id Dissociative
Interchange Narrow, ∆S –
For short lived
K
 L5MX + Y W (L5MX,Y)
Intermediate, or TS

Potential Energy
ML5X +Y
k2
 (L5MX,Y) → (L5MY,X) [ML5Y,X]
ML5Y
fast
 (L5MY,X) → L5MY +X
Reaction Coordinate

 The magnitude of K depends on the ionic charge being


larger when Y and the metal complex are of opposite
charge.
 The likelihood of Y present in the outersphere depends
on [Y], as indicated in step 1.
Rate Law for Dissociative Interchange
 The experimental parameter accessible here is the initial
concentration of the reactant complex [L5MX]0 which in
solution containing Y exists partly in the form of
outersphere complex
 [L5MX]0 = [L5MX] + [L5MX,Y]
 K = k1/k2 = [L5MX,Y]/[Y][L5MX]
 ∴ [L5MX,Y] = K[Y][L5MX]
 & [L5MX]0 = [L5MX] + K[Y][L5MX]
 Hence
 [L5MX] = [L5MX]0/(1 + K[Y])
 Rate = -dL5MX/dt = k2[L5MX,Y]
 Rate = k2K[L5MX]0[Y]/(1 + K[Y])
Associative (a) Mechanism
k1

 L5MX + Y W
k-1
L5MXY
k2
 L5MXY → L5MY + X
 Rate = k1[L5MX][Y]/(k-1 +k2)

 No example for Oh
Associative Interchange (Ia) Mechanism

L5M-X → L5 M— X → L5 M….X

.
∆ +Y


Activation Energy
Vibrational Energy Y


-X
L5M-Y L5M…...X
Y

Key: M-Y bond starts to form before M-X bond


starts to cleave.
 The entering group (Y) is strongly bound, and rate is
sensitive to Y. Implication is that the entering group
and leaving group are strongly bound in the transition
state. This is known as Associative interchange. (Ia)
Summary
Inorganic Reaction Mechanisms

d a intimate

d Id a Ia
SN1(lim) SN1 SN2 SN2(lim)*
Stoichiometric
SN1 & SN2 are not good models for inorganic
reaction mechanisms.*
Summary
L5MX + Y W L5MY + X
Rate = a[L5MX][Y]/(1 + b[Y])
Limiting conditions:
1. b[Y] >>1; ∴ the reaction should be first
order.
2. b[Y]<<1; ∴ the reaction should be second
order.
3. b[Y]=1 ∴ the reaction should be of mixed
order.
A always second order as long as the final step is
not reversible.
Substitution inert ions

 Co3+, Cr3+, Rh3+, Ir3+, Pt4+ & Ni2+


Intimate Mechanisms
 Nature of leaving & entering groups
L5M-X W L5M + X
 For dissociative mechanism rate is dependent
the leaving group
i.e. M-X bond strength
 e- - donor σ-donor like NH3, H-,
π-donor→ σ + filled π-orbital
e.g. Br-, O-, Cp-, RO-, RN2-
 e--acceptor→ σ-donor + empty π*
orbitals e.g. CO
Ligands
 σ-donors

 H->PR3>SCN->I->CH3-,CO>CN->Br->Cl-
>NH3>OH-

 π-acceptors –

 CO~C2H4>CN->NO2->NCS->I->Br-
Leaving group order for Oh
compounds
HCO3->> NO3-> I-~ H2O~ Br->Cl-~
SO42-> SCN->F->CH3COO->NCS-
>NO2->NH3>OH->CN-
Size of the Coordination Sphere &
Metal ION
 Large Coordination sphere favors associative
mechanism
 Small Coordination sphere favors dissociative d-
type pathway.
 e.g. 1st → Oh favors D-type
2nd → Oh may be A-type
3rd → Oh favors A-type
Compare water exchange in [Rh(H2O)6]3+ &
[Ir(H2O)6]3+ 1:3
Coordination Sphere

Coordinatively saturated Coordinatively unsaturated


Favors D- type Favors A-type
Mechanism
 1. Leaving group
e.g.
[Co(NH3)5X]2+ +H2O→ [Co(NH3)5(H2O)]3+
[Co(NH3)5(H2O]3++Y- → [Co(NH3)5(Y)]2+

 Rate is dependent on leaving group and is


independent on entering group.
 i.e. Co-X bond breaking is the rate determining
step.
 Evidence?
Aquation or acid hydrolysis
 Aquation or acid hydrolysis

L5MXn+ + H2O→ [L5M(H2O)]n+1 +X-


 Anation

[L5M(H2O)]n+1 + Y- →L5MYn+ + H2O


Rate constants for acid aquation of some Oh compounds
of Co(III) of the type [Co(NH3)5(X)]2+ at 25 C

Compound k (sec-1)

[Co(NH3)5(OP(OCH3)3)]3+ 2.5x10-4 Note: k


depends
[Co(NH3)5(NO3)]2+ 2.7x10-5 heavily
[Co(NH3)5(I)]2+ 8.3x10-6 On leaving
group X
[Co(NH3)5(H2O)]3+ 5.8x10-6
[Co(NH3)5(Cl)]2+ 1.7x10-6 ∴Confirm
[Co(NH3)5(SO4)]+ 1.2x10-6 Dissociative
pathway
[Co(NH3)5(F)]2+ 8.6x10-8
[Co(NH3)5(N3)]2+ 2.1x10-9
[Co(NH3)5(NCS)]2+ 5.0x10-10
Limiting Rate constants for anation by Yn- and water
exchange (ke) at 45 C [Co(NH3)5(H2O)]3+

Yn- k (sec-1) k/ke Rate is insensitive to entering


group

H2O 100x10-6 -
i.e. evidence support D-
N3- 100x10-6 1.0 activation
SO42- 24x10-6 0.24 Further evidence come from
Cl- 21x10-6 0.21 the substitution studies of Y-
by X-
NCS- 16x10-6 0.16 Where no direct substitution
was
H2O 5.8x10-6 - Observed.
H2PO4- 7.7x10-7 0.13
Example
 [Ru(edta)(H2O)]- + L → [Ru(edta)L]
 [Ru(edta)L] + H2O→ [Ru(edta)(H2O)]+ L

 Rate constants for substitution by L(kl) of


[Ru(edta)(H2O)]- and for aquation kaq of
[Ru(edta)(H2O)]-at 25ºC

 L kL(M-1sec-1) kaq(sec-1)
 Pyridine 6.3x103 0.061
 NCS- 2.7x102 0.5
 CH3CN 3.0x10 3.2
Ligands

COO-

-OOC COO-

N N N
COO-

pyridine edta
Steric Effect of Inert Ligands

 Crowding around the metal ion will


retard the rate of reactions that occur
by an a-type mechanism and to speed
up those occurring via a d-type
mechanism.
Steric Effect
N N
H H
H H
N N

CH3
H3C
CH3
N N
H H
H H
N N
H3C
CH3
H3C

H3C
CH3

N N
H H
H H
N N

H3C CH3
Electronic Effect of Inert Ligands
N N
N N

N - Co L - Co +
+

- L + N
N N

π-donation by a cis ligand π-otbital of trans ligand


into the p component of is ┴ to d2sp3 hybrid.
an empty d2sp3 hybrid.
Rearrangement

N N

- Co +

N
+
N L
-

π-donation from trans Ligand can occur upon rearrangement to


Trogonal bipyramidal
Activation Parameters
 ∆H‡ Enthalpy of activation is a measure of the
height of the energy barrier, particularly bond
strengths within and between reactants, which
must be overcome to attain the transition state;
 If ∆H# <D(M-X), then bond is broken during
activation wher D = dissociation energy.
 ∆S‡ relates to probability of reaction-it includes
contributions from steric bulkand orientation of
reactants
 ∆S‡ ~ 0 for unimolecular reactions
+ for dissociative
 The more negative the value of
 ∆S‡ the lower the reaction rate.
Activation Parameters
 k α ∆G0; more thermodynamically favored reactions proceed faster
 Hamond’s postulate: Two consecutively occurring states that have similar energy
along a reaction coordinate will involve only small structural reorganization.
logk, sec-1

∆G0 = -RTlnK

logK

 Slope = 1 for dissociative; i.e. TS or intermediate falls late in the reaction


coordinate; i.e. product-like
 Slope ~ 0.5 for associative, TS or [x] falls early in the reaction coordinate;
i.e. reactants-like.
 Volume of activation + dissociative & - associative
Activation Parameters, The Eyring Equation
 k = RT/Nhe∆S‡/Re-∆H‡/RT
 kNh/RT = e∆S‡/Re-∆H‡/RT
 keff = e∆S‡/Re-∆H‡/RT
Where N is Avogadro’s Numbern= 6.02x1023 mol-1
H = Plank’s constant = 6.6x10-34 J.S.

∆H‡/R
Slope = -∆
Note : ∆H‡ = Ea -RT
lnkeff

-1
1/T, K
Ligand Substitution Reactions on
Square Planar Complexes
d8 metal ions such as [AuIII, NiII, PdII, PtII,
RhI and IrI ] usually form four coordinate
square planar compounds, especially with
strong ligands.
X
L
M
L L
ML3X + Y → ML3Y + X

Rate = k1[ML3X] + k2[Y][ML3X]


Mechanism for Sq. Substitution
Y Y
L L L L
L L L
M
+Y L L
M M M
L L M
X L X L Y
L L Y
X
X
tbp

 Trigonal bipyramidal may be an intermediate


for A type of TS for Ia
 5-coordinate species may be isolated as in
[Ni(CN)5]3- and can be isolated as salt of
[Co(en)3]3+
 Reactivity order NiII>PdII>PtII
 Nucleophilicity order for square planar
compounds:
CN-~CO>PR3>H->I->Cl->H2O
 Leaving group order
H2O>Cl->I->H->PR3>CO~CN-
Rate Law
 Rate = (k1 + k2[Y])[ML3X]
 Indicate two parallel reaction paths.
 In the presence of a large excess of the entering
ligand [Y] remains constant throughout the reaction
 Rate = -d[ML3X]/dt = kobs.[ML3X] where kobs. =k1
+k2[Y]

 A plot of kobs. versus [Y],

 Straight line with k1 = intercept and k2 is the


nucleophilicity strength of Y.
Rates of reaction of

SCN-
kobs = k1 + k2[Y]

I-
kobs, sec-1

C6H5SH Br--
NH2OH
N3-
NO2-

[Y]
 Rate of reaction of trans-[Pt(py)2Cl2 in methanol @ 30 C as a
function of the concentration of entering ligand.
Rate Law
 Note all ligands have the same intercept, k1,
implying that they go through the same species.
 k2 is different from one ligand to another.
 Since the only species present in solution in
addition to the ligands is the solvent molecules
this implies that the solvent is involved in the
first term and the second term in the ligand
participation
Summary
 Two pathways are involved:
 (1) first order in complex (k1), does not
involve Y in rate determining step. This
mechanistic pathway is solvent mediated.
 (2) first order in complex and Y (k2), Y
involved in rate determining step
Mechanism
L L
K1, slow S
L Pt X +S L Pt
X
L Y- L
fast
L

L Pt Y

Pathway #1 L
Pathway 2
L L
k2, slow Y
L Pt X +Y L Pt
X
L X- L
fast
L

L Pt Y

L
Summary
 Both reactions proceed via an associative
process (A), involving a trigonal bipyramid
transition state. Is there any chemical
justification for this transition state?
 (i) Many five coordinate transition metal
complexes are known, e.g., Fe(CO)5,
[CoL2(CO)3] + , [Ni(CN)5]3-
 (ii) ML3X complexes are sterically and
electronically unsaturated and have space for
Y to coordinate.
Evidence
 Rate law is consistent with associative
mechanism
 Charge on the metal center-has no effect on
the rate of reaction
 Steric effect-significant increase in rate was
observed for less hindered ligands, trans- is
faster than cis
 C6H5>2Me-C6H4>2,4,6-Me3-C6H2-
 Note trans>cis
 For the substitution reaction
 Pt(PEt3)2RCl + Y- → Pt(PEt3)2RY + Cl-
Rate law

ML3X S = solvent
Y

S ML3Y
Y

ML3S

 Schematic representation of parallel


reactions
Effect of Entering & Leaving
Ligands on Rate
 Rate constants for ligand displacement in some
square planar Pt(II) compounds
 Trans-[Pt(py)2Cl2 + Y → trans[Pt(py)2YCl] + Cl-
 Y TC k2(M-1sec-1) nPt
 CH3OH 25 2.7x10-7 00
 CH3O- 25 very slow <2.4
 Cl- 30 4.5x10-4 3.04
 NH3 30 4.7x10-4 3.07
 N 3- 30 1.55x10-3 3.58
 I- 30 1.07x10-1 5.46
 CN- 25 4.00 7.14
 PPh3 25 249 8.93
Effect of Entering & Leaving
Ligands on Rate
 Rate constants for ligand displacement in
some square planar Pt(II) compounds
 trans-[Pt(dien)X]+ + py →
trans[Pt(dien)(py)]2+ + X
 X kobs(M-1sec-1)
 CN- 1.7x10-8
 SCN- 3.0x10-7
 I- 1.0x10-5
 Cl- 3.5x10-5
 H2O 1.9x10-3
 NO3- very fast
Factors affecting rate of substitution
1. Nucleophilicity
 PtCl2Py2 + Y - → PtClYPy2 + Cl-
 Standard Reaction, and methanol as a standard
nucleophile, a base with unshared pair of
electrons such as NH3, I-, Cl-, R-, PR3
 nPt = logk2(Y)/k1(CH3OH) = logk2(Y) –
logk1(CH3OH)
 Factors Affect Nucleophilicity
 Basicity
 Oxidation potential of Y
Nucleophilicity order
 snPt = logk2(Y)/k2(solvent)
 S = nucleophilicity discriminating factor
 I - > Br - > Cl - >> F -
 PR3 > AsR3 > SbR3 >> NR3
 Sulphur > Oxygen

 Soft bases are better nucleophiles for PtII as


it is a soft acid
Trans –ligands & trans effect

 "The trans effect is defined as the


 effect of a coordinated ligand upon the rate of
substitution of ligands opposite to it.“

 For Pt II compounds the order of trans effect


 H2O ~ OH - ~ NH3 ~ NR3 < Cl - ~ Br - < SCN -
~ I - ~ NO2 - ~ C6H5 - < CH3 - < PR3 ~ AsR3 ~
H - < olefins ~ CO ~ CN-
-
NH3 NH3
Cl-
NH3 Pt NH3 NH3 Pt NH3

NH3 Cl
Cl-
Cl
--

NH3 Pt NH3

Cl
Trans effect in synthesis
Cl NH3
NH3
Cl Pt Cl Cl Pt Cl

Cl Cl

NH3
NH3

NH3 Pt Cl

Cl
Try

 Synthesis of cis and trans- isomers of


[PtCl2(NH3)(PPh3)] given the reactants
PPh3, NH3 and [PtCl4]2-
Origin of the trans-effect-

 Electronic (Molecular Orbitals)


 σ-donor ligands such as H-, R-, increase
electron density around the metal.
 π-acceptor ligands such as CO, CN-, PR3, p-
back bonding weaken the bond trans to it.
Trans-effect
T.S. Tpy σ-donor π-acceptor

PR3

PR3

M
T

Ground state X

M
Steric Effect of Inert Ligands
 Steric effect is unclear
 Trans-Pt(PEt3)2RCl] + y → trans-[Pt(PEt3)2RY] + Cl-

 R Solvent Y=CN Y =SC(NH2)2


 C6H5 methanol 3.61 3.30
 C6H5 DMSO very fast 0.532
 o-C6H4CH3 methanol 0.234 0.652
 o-C6H4CH3 dmso 3.54 0.106
 2,6-C6H3(CH3)2 methanol 8.49x10-3 4.94x10-2
 2,6-C6H3(CH3)2 dmso 3.17x10-2 9.52x10-3
Steric Effect

 Steric effect is significant, hints to dissociative


pathway,
 i.e. although associative pathway is feasible but
dissociative pathway may become operative in
the presence of bulky Ligands.
Conclusion
 (i) 1 st order in substrate and nucleophile,
 (ii) k1 (solvent) and k2 (entering ligand)- solvent is
important
 A number of factors determine reactivity
 (i) Nucleophilicity - different from basicity
 (ii) cis and trans effects - kinetic effects, not the
same as trans influence - thermodynamic effect
 (iii) Leaving group effect
 (iv) Rate depends on the metal M
 Predictive synthesis.
Redox Reactions
 Electron-transfer
 A + B- → A- + B
 1. Inner sphere
 Transition state involve interpenetrationg coordination sphere or
bridging ligands or interaction between reactants which is
common to both coordination sphere & serves as channel
through which electron flows.

Taube & Meyer Cr2+ & Cr3+


Co(H2O)62+ (Labile) & [Cr(NH3)5Cl]2+ (innert)
H+
Co(H2O)62+ + [Cr(NH3)5Cl] → [Co(H2O)6]2+ +
2+ [ClCr(H2O)6]2+ +
5NH4+
Inner sphere
 [Co(NH3)5Cl]2+ + Cr2+ W [Co(NH3)5ClCr]4+
 [Co(NH3)5ClCr]4+ → CrCl2+ + [Co(NH3)5]2+
 [Co(NH3)5]2+ + 5H+ W Co2+ + 5NH4+

 Cr3+ inert to substitution with


 k = 2.9x10-8 M-1sec-1 for Cl- anation of Cr3+
 For the reduction k = 6x105 M-1sec-1
 ∴ Cr-Cl could not have been formed from
substitution of free Cl-
Outer-sphere Electron Transfer
 The interaction between the oxidant and
reductant at the time of electron transfer is
small, therefore the coordination shells are
intact; i.e. through space , diffusion control

A e- B-
Example Outer-sphere Electron
Transfer
 [Fe(me2bipy) 3]2+ + [Fe(bipy) 3]3+ W
[Fe(me2bipy) 3]3+ + [Fe(bipy) 3]2+

 Rate = k [Fe(me2bipy) 3]2+ [Fe(bipy) 3]3+

 = 108 M-1sec-1

 Rate of substitution is ~ 104 M-1sec-1

 For outer sphere the redox rate must be


faster than the substitution rate.