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Core Module 7
Richard Douthwaite
R
R P
P
P
1
2
3
reaction coordinate
Inorganic Mechanisms II
6 lectures + 1 workshop - Module 7
Synopsis
Lecture 1: Outer sphere electron transfer I
Workshop
Understand distinction between outer sphere and inner sphere electron transfer.
Describe how rearrangement of solvent and internal atom coordinates affects the rate of
outer sphere electron transfer.
Use the Marcus cross relation and discuss the relation ship between , G and Go
Understand that a bridging group (atom or molecule) is required for inner sphere electron
transfer.
Distinguish factors that indicate if electron transfer occurs by an outer or inner sphere
mechanism.
Understand what a catalyst is and the principal ways that a catalyst affects the rate of a
chemical reaction.
Understand the concept of the catalytic cycle and the principle of microscopic reverse.
Illustrate the basic mechanisms of some catalytic reactions incorporating alkenes.
Illustrate the basic mechanisms of some catalytic reaction incorporating alkanes.
Bibliography:
Electron transfer:
J. E. Huheey, E A Keiter and R. L. Keiter. Inorganic Chemistry, 4th Ed., 1993, p 547 576.
R. A. Henderson. The Mechanisms of Reactions at Transition Metal Sites, 1995
R. B. Jordan, Reaction Mechanisms of Inorganic and Organometallic Systems, 1991 Ch 3 and 6.
R. A. Marcus, Angew. Chem. Int. Ed. 1993, 32, 1111.
Catalysis:
C. Elschenbroich and A Salzer. Organometallics, 2nd Ed.,1992, Ch 17
F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 5th Ed.
Chen, H et al. Science, 2000, 287, p1995
R. B. Jordan, Reaction Mechanisms of Inorganic and Organometallic Systems, 1991 Ch 5.
Associated Core Courses
AKDK
JML
SBD
MCRC
RED
JML
AKDK
PBK
RNP
1st year
2nd year
2nd year
2nd year
2nd year
3rd year
3rd year
3rd year
3rd year
We will be considering electron transfer between inorganic complexes. There are two mechanisms
by which inorganic complexes transfer electrons. The outer sphere mechanism and the inner
sphere mechanism. The outer sphere mechanism is important because of the analogy that can be
drawn between electron transfer in metal complexes and electron transfer in metalloenzymes. The
inner sphere mechanism is important because atom transfer (bond breaking/formation) can be
concomitant with electron transfer. Both are important for photosynthesis.
Outer sphere electron transfer occurs between complexes that do not undergo substitution. No new
bonds are broken or formed.
Inner sphere electron transfer occurs between complexes via a bridging ligand. At least one of the
complexes needs to be labile to allow the bridge to form. Bonds are broken and formed.
Recap
Inert
Labile
Most Co(III)
Most Co(II)
oxidant (O)
is reduced
M'b+Ly
Ma+Lx
M'(b+1)+Ly
reductant (R)
is oxidised
Mechanism
1. Formation of precursor complex
(a+1)+
Lx
' b+
Ly
Keq
M(a+1)+Lx
M' b+Ly
Precursor complex
M' b+Ly
M(a+1)+Lx
kET
M' (b+1)+Ly
Ma+Lx
Successor complex
Ma+Lx
M' (b+1)+Ly
kdiss
Ma+Lx
M' (b+1)+Ly
Formation of precursor complex and dissociation of successor complex are fast. Electron transfer slow
G
GET
reactants
precursor
complex
successor
complex
reaction coordinate
5
products
2+
[Ru*(NH3)6]3+ + [Ru(NH3)6]
[Ru*(NH3)6]2+ + [Ru(NH3)6]3+
[Ru(NH3)6]3+/2+ E0 = +0.051V
-9
2+
[Co*(NH3)6]
+ [Co(NH3)6]
reactions (M and
M* are isotopes).
-1 -1
k = 10 M s
3+
Self exchange
Go = O
[Co*(NH3)6]3+ + [Co(NH3)6]2+
[Co(NH3)6]3+/2+ E0 = +0.058 V
k = 1.3 x 103 M-1s-1
[V(H2O)6]2+
[V(H2O)6]3+
[Ru(NH3)6]3+
2+
+ [Ru(NH3)6]
Cross reaction
[V(H2O)6]3+/2+ E0 = -0.255 V
Gt
Go
energy needed
for solvent
reorganisation
energy to bring
reactants together
(including overcoming
coulombic repulsion)
Gi
i)
S
S
S
L
L
M*
II
L
M
III
L
L
S
S
S S
S
S
S S
a+
b+
S
S
OH2
OH2
(a +b)+
S
S
S
M
M*
S
H
O
OH
S
2
2
H2O
OH2
OH2
S
S
OH2
S
S S S S S
S S
S S
S
S
S S
H 2O
II
OH2 H2O
III
OH2
precursor complex
Solvents that interact strongly with complexes (e.g. via hydrogen bonding) will reduce the rate of
electron transfer
ii)
Gi. Metal-ligand bond lengths will change when the oxidation state of the metal changes.
The Frank-Condon principle states that because nuclei are much more massive than electrons, an
electronic transition occurs much faster than the nuclei can respond. Complexes must adjust their
M-L bond lengths before electron transfer.
6
OH2
H2O
Fe*II
H2O
H2O
Fe*II
FeIII
OH2
OH2
OH2
FeIII
Identical bond
lengths in T.S.
OH2
OH2
OH2
OH2 H2O
OH2 H2O
H2O
OH2 H2O
OH2 H2O
Fe(III)-O = 2.05
Fe(II)-O = 2.21
OH2
OH2
OH2
OH2
OH2
H2O
OH2
H2O
OH2
Fe*III
OH2 H2O
OH2
FeII
OH2 H O
2
OH2
OH2
OH2
e-
Fe-O
compression
Fe-O
elongation
Orbital energies must be of equal for electron transfer to occur (but not sole requirement)
R
P
G
P
1. Where did energy come from to 'activate' the electron ?
2. R
ET
P*
relax
P + heat
Reaction coordinate
Self exhange
R
P
R
P
I
I
G
r
rR
GO
rR
rP
rP
At I, the requirement of equal orbital energies is met allowing the possibility of electron transfer.
How does electron move from reactant to product?
At I, electronic-vibrational coupling (Ec) determines the probability el (transmission coefficient)
that an electron will transfer. el increases with increasing Ec.
P
rR
r
rR
rP
GO
r
rP
r
8
Configuration
k (M-1 s-1)
[Cr(H2O)6]2+ / [Cr(H2O)6]3+
t2g3eg1 / t2g3eg0
10-5
0.3
[V(H2O)6]2+ / [V(H2O)6]3+
t2g3eg0 / t2g2eg0
10-2
0.2
[Fe(H2O)6]2+ / [Fe(H2O)6]3+
t2g4eg2 / t2g3eg2
0.15
[Ru(H2O)6]2+ / [Ru(H2O)6]3+
t2g6eg0 / t2g5eg0
4 x 103
0.05
[Fe(phen)3]2+ / [Fe(phen)3]3+
t2g6eg0 / t2g5eg0
103
0.01
Electron transfer requires orbital overlap and occurs between orbitals of the same symmetry
e-
eg
t2g
Cr2+
Cr3+
Cr3+
Cr2+
Orbital symmetry
In Oh field eg is *: eg eg transition = large change in bond length. Slow electron transfer
L
L
L
L
In Oh field t2g is *: t2g t2g transition = small change in bond length. Fast electron transfer
L
L
L
L
Overlap
2nd and 3rd row metals generally faster that 1st row due to better overlap of 4d and 5d orbitals. (Also
due to stronger ligand fields bond length distortions will be smaller).
Ligands that have extended -systems e.g. Phen, bipy etc can assist electron transfer.
Bipy
Phen
Electronic Configuration
Energy is required if a complex has to change electron configuration to allow electron transfer.
e.g.
2+
NH3
H3N
CoII
H3N
NH3
H3N
CoIII
NH3 H3N
NH3
3+
NH3
3+
NH3
NH3
H3N
NH3
CoIII
H3N
NH3
NH3
NH3
H3N
CoII
NH3 H3N
NH3
2+
NH3
NH3
NH3
e-
10
+
G =
2
4
Go
1+
w = work term (energy required to bring two reactants together), = total reorganisation energy
(includes solvent reorganisation and bond length changes of reactants)
For many reactions involving complexes of same charge or if the reactants are effectively fixed in
space such as in a protein w 0. Therefore
G =
4
Go
1+
2
and for a self exchange reaction Go = 0.
G =
4
reaction coordinate
Recap
Eyring equation relates rate constants and free energy of activation
k =
kBT eG /RT
h
G
Go
reaction coordinate
whenGo = G = 0
and Go < G > 0
Normal
Region
Marcus Inverted
Region
k s-1
Go
Go (eV)
In the inverted region the rate (k) decreases as the thermodynamic driving force increases!
R P
P
P
2. G = 0
1
Go 3 > 2 > 1
reaction coordinate
The Marcus inverted region is probably important in photosynthesis where wasteful back
electron transfer reactions (which are highly exothermic) are prevented.
12
Marcus cross-relation
Self exchange reaction Go = 0
cross reaction Go < 0
Marcus related the cross reaction to the two self exchange reactions.
(log KAB)2
fAB =
4 log kAAkBB
1/2
kAB = (kAAkBBKABfAB)
Z2
kAB = rate of cross reaction: kAA, kBB = self exchange rates: KAB = equilibrium constant of reaction
Z = collision frequency for hypothetical uncharged complex (1011-1013 M-1s-1). Can calculate the rate
of electron transfer cross reaction k12 if other parameters are known.
kAB
or
GAB
(kAAkBBKAB)
1/2
1
2
e.g.
MnO4O
MnO4-
Fe(CN)64R
e
+
+
Fe(CN)63- +
e-
MnO4- + MnO42-
kAA
Fe(CN)63- + Fe(CN)64-
kBB
kAB = ?
MnO42- +
0
MnO42- E = 0.56V
Fe(CN)64- E0 = 0.36V
MnO42- + MnO4
andGo = -nF
therefore -RTlnK = -nF
3-1 -1
Fe(CN)64- + Fe(CN)6 kBB = 300 M s
Rem: Go = -RTlnK
KAB=
Fe(CN)63-
( O - R )
(38.94(0.56 - 0.36))
K=
nF
RT
= 2.4 x 103
13
Reactants
[Co(Phen)3]3+ + [Ru(NH3)6]2+
3.5 x 10-5
1.5 x 10-4
[Co(en)3]3+ + [V(H2O)6]2+
3.1 x 10-3
5.8 x 10-4
[Ru(NH3)6]3+ + [V(H2O)6]2+
2.2 x 103
1.3 x 103
[Fe(H2O)6]3+ + [V(H2O)6]2+
1.6 x 106
1.8 x 104
[Fe(H2O)6]3+ + [Ru(NH3)6]2+
1.0 x 108
3.4 x 105
k =
kBT eG /RT
h
k T G /RT
vs k = el B e
h
"adiabatic"
"nonadiabatic"
14
MIIIL5X
ka
M' IIY5
L5MIII X
M' IIY5 + Y
kET
L5MII
M' IIIY5
kd
L5MIIY
XM' IIIY5
L5MIIX
M' IIIY6
k-a
M' IIY5
L5MIII X
II
Y + L 5M
M' IIIY5
or Y + L5MII
M' IIIY5
[Co*(NH3)6]3+ +
t2g6
[Co(H2O)6]2+ +
[Cr(H2O)6]2+
[Cr(H2O)6]3+
t2g5eg2
t2g3eg1
t2g3
6 NH3
k = 10-3 M-1s-1
[Co(H2O)6]2+ +
[Cr(H2O)6]2+
t2g6
t2g3eg1
t2g5eg2
inert
labile
labile
[Cr(H2O)5Cl]2+ +
t2g3
k = 6 x 105 M-1s-1
inert
-
Co
NH3
H2O
NH3
Cl
Cr
OH2
4+
H2O
H2O
H2O
5 NH3
[IrCl6]2t2g5
[Cr(H2O)6]2+
[IrCl6]3-
Cl
Cl
[Cr(H2O)6]3+
t2g6
t2g3eg1
Cl
H 2O
Cl
Ir
Cl
Cl
OH2
Cr
t2g3
H2 O
H 2O
H 2O
Factors that affect the rate of inner sphere electron transfer reactions
ET
bridging
complex
scission
bridging
complex
formation
G
L Assoc
L Diss
reaction coordinate
Self Exchange
i) Formation of the bridging complex can be the rate limiting step (ka). This will be dependent on
how inert or labile the complexes are. (kET vs ka). It is also possible that dissociation (kd) is the rate
limiting step.
16
bridging
complex
formation
ET
bridging
complex
cission
L Diss
L Assoc
reaction coordinate
ii) Electronic configurations. * (eg) orbitals interact strongly with bridging ligand. Orbital
symmetries of metal * and bridging ligands facilitate electron transfer. Massive acceleration in
rates from outer to inner sphere can be achieved.
Reaction
HOMO
LUMO
Acceleration IS/OS
Cr2+ + Co3+
~ 1010
Cr2+ + Ru3+
~ 102
V2+ + Co3+
~ 104
V2+ + Ru3+
All OS
Cr2+ Ru3+
Reorganisation of Ru3+
less than Co3+
Cr2+
Co3+
Large reorganisation
3+
for Co
OS. IS much
V2+
Co3+
Co3+ Reorganisation
IS faster
faster
L
e.g.
Cl
L
L
M(
M(
17
V2+
Ru3+
Easily go OS.
No reorganisation
iii) Bridging ligand. Inner sphere electron transfer is very sensitive to bridging ligand.
1) The bridge connects the two metals.
+
2+
(NH3)5Co
(NH3)5Co
+ Cr2+(aq)
Cr3+(aq)
O
Cr2+(aq)
R= H
Me
Ph
7.2
0.35
0.15
k M-1s-1
Bu
9.6 x 10-3
2) Transfer can be a two step process from metal to ligand then ligand to metal. This
circumvents the simultaneous reorganisation energy of both complexes that is required for
outer sphere.
k = 4 x 10-3 M-1s-1
3+
(NH3)5Co
III
+ Cr
(NH3)5CoIII N
(NH3)5Co
(aq)
+ Cr3+(aq)
k = 17.4 M-1s-1
3+
Coordination of Cr2+
2+
NH2
2+
Must be OS
2+
+ Cr
(aq)
IS
(NH3)5CoII N
O
NH2
Cr2+(aq)
5+
(NH3)5CoIII N
O
NH2
Cr3+(aq)
18
2+
3+
+ Cr (aq)
A good test is to compare electron transfer rates of N3- and NCS- complexes.
E (Go s)of N3- and NCS- complexes are similar.
If kN3- / kNCS- ~ 1 (OS). If kN3- / kNCS- >> 1 (IS). This is because N3- is symmetric.
O
kN3- / kNCS-
rxn type
[(NH3)5CoX]2+
Cr2+
104
IS
[(NH3)5CoX]2+
V2+
27
intermediate
[(NH3)5CoX]2+
Fe2+
> 3 x 103
IS
[(NH3)5CoX]2+
Cr(bipy)32+
OS
[(H2O)5CoX]2+
Cr2+
4 x 104
IS
M-N=N=N-M
M-N=C=S-M
19
Catalysis
Catalysis is involved in the production of approximately 90% of the chemicals currently used
in industry and forms the basis of technologies designed to remove or prevent noxious
chemicals detrimental to the environment. Through the action of enzymes, catalysis also plays
a central role in the life cycle.
Catalysis is a kinetic phenomenon. A catalyst increases the rate that a reaction reaches
equilibrium but does not affect the position of the equilibrium. If a catalyst changed the
position of equilibrium the second law of thermodynamics would be contravened.
T.S
G
T.S
Gcat
Go
Reactants
Products
reaction coordinate
Amongst other properties, a good catalyst will give high yields of the desired product. i.e the
catalyst affects the product distribution of a reaction. This is not because the catalyst has
changed the position of equilibrium but because most catalytic reactions are run under
non-equilibrium conditions.
20
e.g. asymmetric catalysis. Product enantiomers have the same ground state energy but G s are
different.
Kinetics determines selectivity. No thermodynamic difference between the products
G
reactant
k2
k1
k1 > k2
Enantiomer A
G kJmol
Enantiomer B
-1
14
100oC
12
0 oC
10
-100oC
8
6
4
2
0
0
10
20
30
40
50
80
90
94
95
96
60
70
80
90
97
Me
Me
Me
Me
21
100 k1/k2
98
% ee
H2 N
O
NH2
O
Cu
Cu
N
N
2+
No Cu2+
2. Orbital energy. Perturbation of the reactant orbital energies by interaction with a catalyst
can change reaction rates.
enhanced nucleophilic
substitution
enhanced solvolysis
X
enhanced acidity
steric hindrance
Cr
OC
CO
enhanced acidity
CO
3. Orbital symmetry. A bond forming reaction requires interacting orbitals of the same symmetry.
The frontier molecular orbitals and hence symmetry may change on interaction with a catalyst
symmetry forbidden
H2
H
LUMO
HOMO
HOMO
M
H
LUMO
H
M
H
22
H
M
H
Some Terminology
Precatalyst: The transition metal complex that is added to a reaction. The true catalytic species
usually results from a preliminary reaction or event (e.g. ligand dissociation) of the precatalyst
before binding of the substrate and catalysis can occur.
CO
Ph3P
PPh3
Rh
-PPh3
Ph3P
OC
PPh3
Rh
H
PPh3
(18 e)
(16 e)
Resting state: The catalyst may be in equilibrium with another complex that does not
catalyse the reaction but can act as a reservoir for the catalyst.
Cl
Ph3P
Rh
Cl
Ph3P
Rh
Ph3P
Ph3P
catalyst
PPh3
Rh
Cl
PPh3
resting state
Fundamental Reactions
Dissociation/association, oxidative addition/reductive elimination and insertion/extrusion are
the most common elementary steps that support a catalytic cycle and conform to the principle
of microscopic reverse.
Principle of microscopic reversibility
The mechanism of a reverse reaction must be the same as the mechanism for the forward
reaction under the same conditions. This results because the least energetic pathway in one
direction must be the least energetic pathway in the other direction. i.e. The intermediates and
transition state must be the same in either direction. One consequence of this is that a catalyst
for a forward reaction will be a catalyst for the reverse reaction.
23
10
Ti
Cr
Mn
Fe
Co
Ni
Zr
Nb
Mo
Tc
Ru
Rh
Pd
Hf
Ta
Re
Os
Ir
Pt
fewer d-electrons
high coordination numbers
high oxidation states
oxophilic
prefer hard ligands
Late metals are used in most catalytic reactions involving M-C and M-H bonds (notable
exceptions are Ziegler Natta polymerisation (Ti, Cr) and alkene epoxidation (Ti, Mn)
Also M-H and M-C bonds of the later metals are less sensitive to water and oxygen
24
L(n+1)M - H
CH3
R
R
L nM - H
CH3
R
L nM - H
L nM
R
R
L nM
L nM
LnM - H
LnM-H
LnM
-allyl
Internal alkenes are thermodynamically more stable than terminal alkenes. Isomerisation
gives mixtures of thermodynamic products.
e.g.
Many metal complexes are catalysts for isomerisation. Rhodium catalysts tend to be the most rapid.
25
R3
R1
R3
H
+ H2
R2
R4
R2
R4
R1
R3
R1
R3
+
R2
R2
R4
R3
OH
R2
R4
H2 + CO
R1
R4
Anti-Markovnikov addition
Hydrogenation
Rh(CO)(H)(PPh3)3
(18 e, RhI)
-PPh3
R
R
Ph3P
OC
Rh
H
PPh3
(16 e, RhI)
(18 e, RhI)
CH2CH2R
Ph3P
Rh
OC
Ph3P
Rh
Ph3P
III
H (18 e, Rh )
CO
PPh3
Oxidative addition
RDS (change in
Ox. St.)
(16 e, RhI)
H2
Ph3P
OC
Rh
CH2CH2R
PPh3
Other precatalysts include RhH(PPh3)3, (good for internal and terminal alkenes). Can do
asymmetric.
26
Hydroformylation
Rh(CO)(H)(PPh3)3
-PPh3
O
R
R
H
PPh3
H
Ph3P
OC
Rh
(16 e, RhI)
H
O
CCH2CH2R
Ph3P
Rh
OC
(18 e, RhI)
(18 e, RhIII)
Ph3P
Rh
Ph3P
CO
PPh3
O
Rh
(16 e, RhI)
CCH2CH2R
PPh3
CH2CH2R
PPh3
Rh
OC
(18 e, RhI)
CO
CO
Ph3P
OC
CH2CH2R
PPh3
Rh
Other common precatalyst is Co2(CO)8 (Otto Roelen 1938 discovered hydroformylation using
this precatalyst). Isomerisation and hydrogenation can be competitive. Can do asymmetric
hydroformylation.
Isomerisation can be useful. Hydroformylation of terminal alkenes is much quicker than
internal alkenes due to alkene/ligand sterics at metal.
H2/CO
e.g.
(Linear aldehydes
are desired)
Nu
Ph3P
e.g.
Pd
PPh3
OC
27
Nu
OH = acids
OR = esters
NR2 = amides
Alkene/CO copolymerisation
O
Pd(OAc)2
+ CO
OMe
PPh3, TsOH
MeOH
Using chelating bis-phosphines it was found a high molecular weight polyketone was formed.
O
+ CO
Pd(OAc)2
dppp, TsOH
MeOH
PPh2
PPh2
dppp
Ph2
P
(CH2)n
NCMe
2+
2+
NCMe
Pd
P
Ph2
+
N
Pd
NCMe
n = 1-4 (3 best)
N
O
Me
Pd
NCMe
O
[B(3,5-(CF3)2C6H3)4]NCMe
Important features:
i) chelating bidentate ancillary ligands seem to be required
ii) weakly coordinating anions
iii) Electrophilic metal centre required to bind alkene but not too electrophilic or CO binds too
strongly and inhibits copolymerisation.
28
O
Pd
P
Pd
P
+
Pd
CO
CO
Pd
OMe
P
Pd
OMe
O
+
P
CO
Pd
OMe
OMe
etc.
Pd
OMe
CO
CO
Pd
etc.
CO
Pd
Pd
Pd
Pd
OMe
CO
Pd
Pd
P
P
P
Pd
P
29
MeOH
MeO
O
iii) Why is there strict alternation of CO and ethylene in the co-polymer? Double CO or
double ethene defects are rarely observed.
Double CO insertion is thermodynamically unfavourable and will not occur.
Double ethene insertion is thermodynamically favourable by ~ 80 kJ mol-1
An ethene/CO ratio of 10:1 still gives strict alternation until the CO has been consumed.
Explanation: The acyl intermediate coordinates via the carbonyl oxygen to Pd to give a
metallocycle. Formation of the metallocycle has two consequences
1) Prevents double ethene insertion as the ethene is not a strong enough donor to displace the
Pd-O bond and
2) Prevents -H elimination
O
Pol
CO
Pd
Pol
Pd
CO
Pol
Pd
CO
CO
Pd
H
Pol
Pd
Pol
Pd
30
Pol
Pd
Pol
R1
R3
R3
R1
+ H2
H
R2
R2
R4
R4
Bond
C-H
400-415
H-H
432
C=C ()
260-275
Bu (H2 acceptor)
H2
PtBu2
PtBu2
Ir H
Ir
PtBu2
PtBu2
Bu
PtBu2
Ir
PtBu2
Addition of an H2 acceptor helps to drive the reaction by removing H2 and formation of 2 x
C-H bonds (Hrxn 0, thermoneutral reaction)
31
Internal alkenes are more stable than terminal alkenes. Distribution of mainly thermodynamic
products
PMe3
i
Pr3P
Rh
Cl
PMe3
10
27
63
Borylation of alkanes
Organoboranes are very useful intermediates for a large range of organic compounds.
R1
R3
H
R2
O
+
B-H
R4
R3
R1
O
H-Bpin
+ H2
R2
R4
Bond
C-H
400-415
H-H
432
B-H
464
B-C
472
Hrxn = [415 (C-H) + 464 (B-H)] [432 (H-H) + 472 (B-C)] = -25 kJ mol-1 (exothermic)
M= Rh, Ir
O
O
+
B-H
150 oC
O
+ H2
O
+
0.5 [IrCl(COD)]2
B-H
25 - 80 oC
H2
More recently, functionalisation of arenes at room temperature has been achieved. Many
functional groups on the arene can be tolerated.
Ir
PinB
H
e.g.
H
BPin
B-C bond formation could be via oxidative addition of C-H/reductive elimination of B-C or
-bond metathesis
O
H CR3 + M
B
O
O
H
B
O
O
H
CR3
CR3
-bond metathesis
oxidative addition/
reductive elimination
O
R3C
M H
33