Reaction Mechanisms

Before we get into the synthetic chemistry it is a good idea to first become familiar with some
of the more importatn reaction mechanisms available to transition metals. We will see these
again and again as we continue in the course.
I. Ligand Substitution
M

L1

L2

L2

L1

Both associative (SN2-like) and dissociative (SN1-like) mechanisms are possible

II. Oxidative Addition/Reductive Elimination
often polarized,
"electrophilic"

M(n)

oxidative addition
A

metal has been

formally oxidized
A
M(n+2)

reductive elimination
usually low-valent (n = 0,1),
"nucleophilic" metal
coordinatively unsaturated

MA and MB bonds are

usually strong, complex
coordinatively saturated

Reaction Mechanisms
III. Migratory Insertion & Elimination
X

M Y

M Y

note cis
relationship

M Y

note empty
coordination site

IV. Nucleophilic Attack on Ligands Coordinated to Metal

reactive to
nucleophiles
(electron-deficient)

Nuc

M
unreactive to
nucleophiles
(electron-rich)

very reactive to other electrophiles,

reactivity increased
if electron-deficeint

M X

Nuc

often this process results in "reductive

elimination" of the metal

Reaction Mechanisms
V. Transmetallation
M1 R

M2 X

M2 R

M1 X

almost always the rate-limiting step,

usually the culpret when catalytic
processes fail

M1 = Mg, Zn, Zr, B, Hg, Si, Sn, Ge

M2 = transition metal

VI. Electrophilic Attack on Metal Coordinated Ligands

Several different reaction modes are known, will explore further later

Nuc

reductive
elimination
E

Nuc

inverstion at R

retention at R

attack can directly cleave MR bond or

can happen , , or to the metal

Ligand Substitution
Though we will be concerning ourselves more with the reactivity and synthetic utility of organimetallic
complexes, understanding the mechanisms available for ligand substitution is critical to
understanding how the complexes react.
M

L1

L2

L2

L1

Associative Mechansim (SN2-like) typically occurs with coordinatively unsaturated complexes;

exemplified by 16-electron, square planar, d8 metals (Ni(II), Pd(II), Pt(II), Rh (I), Ir (I))

Lc
LT

X
Lc

square
planar
(16 e)

+Y
apical
attack

Lc
LT

Y
M

X
Lc

square
pyramidal
(18 e)

Lc
LT

M
Lc

Lc

LT

trigonal
bipyramidal
(18 e)

Factors that influence the rate:

identity of the metal
identy of incoming and outgoing ligands
identy of the trans ligand ("trans effect")

M
X

Y
Lc

X
apical
exit

Lc
LT

M
X

Y
Lc

Ligand Substitution
Though we will be concerning ourselves more with the reactivity and synthetic utility of organimetallic
complexes, understanding the mechanisms available for ligand substitution is critical to
understanding how the complexes react.
+

L1

L2

L2

L1

Dissociative Mechansim (SN1-like) typically occurs with 18 electron coordinatively saturated

complexes; often slower that associative substitution; exemplified by M(0) metal carbonyl complexes
CO

+L

Ni(CO)4

Ni(CO)3

LNi(CO)3

(d10, 18 e)

(d10, 16 e)

(d10, 18 e)

The rate can be accelerated by bulky ligands (loss of labile ligand relieves steric strain). This is
particularly noticeable with phosphines and can be measured by the "cone angle". The
electronics of the phosphine can be changed (idenpendently from sterics) by substitution.

P
M

cone angle ()

OMe
OPh
Ph
o-tolyl
Cy
t-Bu

107
128
145
194
170
182

co (cm-1)
2079
co (cm-1) is determined with Ni(CO)3L and is a
2085
measurement of the amount of backbonding. More
2069
donating L, more backbonding and co decreases.

2056
2056

Hartwig, Organotransition Metal Chemistry, 2010, pp 3738.

Ligand Substitution
A "full dissociation" is not always necessary to open coordination site on an 18-electron complex.
Sometimes a polydendate ligand can "slip" and free up a coordination site.
This can explain some observations seen with ligands such as 3-allyl, 5-cyclopentadienyl, and 6-arene
complexes. By slipping to a lower hapticity, a coordination site (or two) is opened.

3-allyl
(2 sites)

1-allyl
(2 sites)

6-arene
(3 sites)

4-arene
(2 sites)

2-arene
(1 site)

+L
Mn(CO)3

Mn(I), d6
18 e

Mn(CO)3

Mn(I), d6
16 e

CO
L

Mn(CO)3

Mn(CO)2L

Oxidative Addition/Reductive Elimination

Reactions of this type are central to the synthetic utility of transition metals complexes and relies
on the ability of metals to easily and reversably change oxidation states (compare to what is
takes to change oxidation state of C).
M(n)

oxidative addition
A

A
M(n+2)

reductive elimination

The terms "oxidative addition" and "reductive elimination" are generic and refer only to the process of
changing the oxidation state of the metal. The exact mechanism by which this occurs can vary.
Oxidative Addition (OA)
Metal must be coordinatively unsaturated and relatively electron rich (nucleophilic) and usually in
low oxidation state (0, +1). -Donor ligands (PR3, R, and H) facilitate OA. -Acceptor ligands
(CO, CN, alkenes) suppress OA.
By the formalism used to assign oxidation state, the metal has lost two electrons during the above
process (the metal has been oxidized)
Metals that most commonly undergo OA reactions (other are certainly known):
d10: Ni(0), Pd(0) d8: Ni(II), Pd(II)
d8: Rh(I), Ir(I) d6: Rh(III), Ir(III)
Exact mechanism by which the OA occurs depends on the nature of the substrate.

Oxidative Addition/Reductive Elimination

Nonpolar Electrophiles

Common examples: H2, RH, ArH, R3SiH, R3SnH, R2BH, R3SnSnR3, R2BBR2, RC

Generally undergo OA by concerted, one-step "insertion" mechanism. The configuration of any

stereocenters would be expected to be retained. May require dissociation of a ligand from the
initial complex.
AB
LnM

LnM

LnM

LnM

"agostic" interaction
(2 e, 3 center bond)

cis stereochemistry
(kinetic)

Examples:
OC
Ph3P

Ir

PPh3
Cl

H2

H
Ph3P

Ph3P
Ph3P

Rh

H
Ir
CO

PPh3

Ph3P

Cl

Ph3P

PPh3
Cl

RCHO

Ph3P

Rh

PPh3
Cl

PPh3
Rh
R
Ph3P
Cl
O

R2BH

Ph3P
Ph3P

H
Rh
Cl

PPh3
BR2

Oxidative Addition/Reductive Elimination

Polar Electrophiles
Common examples: HX, X2, RX, R(O)X, ArX,
Two mechanisms are possible. One is analagous to reactions with nonpolar electrophiles (direct
insertion). The other is an ionic, two-step SN2 mechanism, where the metal functions as a
nucleophile and donates two electrons in the process. The configuration of any stereocenters would
be expected to be inverted in this case. The structure of the electrophile determines which is active.

Mn

M(n+2)

relative rates:
Me > primary > secondary >> tertiary
I > Br ~ OTs > Cl >> F
phosphines promote with greater basicity giving faster rates

M C

Oxidative Addition/Reductive Elimination

Polar Electrophiles, cont'd
Examples:
L
OC

Ir

inversion
Cl

CH3I

CH3
L
Cl
Ir
L
OC
I

Pd(0)
Pt-Bu2Me

H
t-Bu

TsO
H

trans
(kinetic)

Br

Ph

trans

t-Bu
H

TsO

Br

L2Pd

L2Pd
H

L2Pd

Br

L2Pd +

Ph

trans
(retention)

Ph

ONa
Ph

Fe(CO)5
d8, 18 e

Ph

Na2[Fe(CO)4]2
Collman's reagent
"supernucleophile"

Na[RFe(CO)4]
Further reactions possible

Oxidative Addition/Reductive Elimination

Polar Electrophiles, cont'd
There are also examples of reactions that cannot be explained by either of these mechanisms
(concerted or SN2). These have been rationalized by a radical-chain mechanism.

h or

O2R

LnMn

M(n+1)Ln

X
R

M(n+1)Ln +

M(n+2)Ln

+ R

sequential 1e oxidations,
net 2e oxidation of metal

Oxidative Addition/Reductive Elimination

M(n)

oxidative addition
A

M(n+2)

reductive elimination

Reductive Elimination (RE)

The reverse of oxidative addition. Concerted mechanism proceeds with retention of any
stereochemical information. Nucleophilic attack on the ligand would invert the configuration.
Factors that influence:
First row metals faster than second row, faster than third row
Electron-poor complexes react faster than electron-rich
Sterically hindered complexes reacter faster
H reacts faster than R
complexes with 1 or 3 L-type ligands faster than 2 or 4
Geometry of the complex is also quite important

Ph

Ph
P

Me
Pd
Me

P
Ph

Ph

fast

Me
Me

Me

Ph2P

Pd
Me

PPh2

no reaction

Migratory Insertion & Eliminations

Migratory Insertion
In this process an unsaturated ligand (CO, RNC, alkene, alkyne) inserts into an existing M-ligand bond.
The two ligands involved must be cis to one another. These are usually reversible processes. At the end
of the reaction the metal is left with an empty coordination site.
X

M Y

M Y

M Y

General examples:
R

+L

LnM

LnM
C

C
O

+L

LnM
A

trans

LnM
A

+L
B

L
LnM
A

trans

cis
R

LnM

R = aryl, alkyl, H

R
B

Migratory Insertion & Eliminations

Eliminations are the reverse reaction of migratory insertion and can occur one after the other.
The group being eliminated does not have to be the one that participated in the insertion.
There are several types of eliminations.
-Hydride Elimination (BHE)
If an alkyl metal complex has hydrogens b to the metal, then this type of elimination is likely to
occur. However, the -hydrogens usually must be syn coplanar to the metal. Also the metal
usually must have an open coordination site.

H
LnM

LnM

LnM

syn coplanar
BHE from transition metal-alkoxides and -amines are also important
Me
O
LnM

Me

O
LnM

Me

+L

Me
H

L
LnM

MH without using H2
-Eliminations of alkoxides and halides are known.

Me

Me

Migratory Insertion & Eliminations

Eliminations are the reverse reaction of migratory insertion and can occur one after the other.
The group being eliminated does not have to be the one that participated in the insertion.
There are several types of eliminations.
-Hydride Elimination (AHE)
Elimination of an -hydrogen from metal alkyl complexes. This forms a carbene. Much slower
than -elimination processes and usually only occur when BHE is not possible. More common
with early transition metals (d0, group 4 and 6), but can happen with later metals.

H
LnM

LnM

Often induced by ligand exchange processes.

Cp
Me3P

t-Bu

t-Bu

Me
Me2P

PMe2

Me Cp
V

P
P
Me

Me

t-Bu

+ tBuCH3 + PMe3

Nucleophilic Attack on Coordinated Ligands

Many different kinds of examples of this. From our prespective the more important ones
involve attack on MCO complexes and Malkene/alkyne complexes.
Attack on Metal-Bound Carbonyl The nucleophile is typically strong nucleophiles, like RLi

LnM C

RLi

LnM

Ln is good -acceptor
(another CO)

usually quite stable and can

be further manipulated

acyl "ate" complex

Attack on MC -Bonds Such bonds are often intermediates in catalytic reactions. The carbon can
be sp2 or sp3 hybridized. Nucleophilc reactions with 3-allyl complexes fall in this category. Can also
be considered as a "reductive elimination" process.
X
L

ROH

Pd

Ar

PdLn

ArCO2R
Nuc

Nuc
M

HX

Nucleophilic Attack on Coordinated Ligands

Many different kinds of examples of this. From our prespective the more important ones
involve attack on MCO complexes and Malkene/alkyne complexes.
Attack on MC -Bonds By ligating the metal, alkenes and alkynes usually become electrophilic.
This makes then susceptible to nucelophilic attack. Depending on how the nucleophile reacts, the
addition can be syn or anti.
Nuc

Nuc

"external" addition of nucleophile

product of anti addition
(most common pathway)

Nuc
insertion
M

Nuc

"internal" addition of nucleophile

product of syn addition
M

Nuc

Other nucleophilic reactions will be covered as needed

Transmetallation
Importance is growing as this is a key step in useful methods for constructing CC bonds, particularly
such bonds that are difficult to forge by other means. However, the exact mechanism by which
transmetallation occurs is not well understood and seems to be quite dependent on the metal species.
M1 R

M2 X

M2 R

M1 X

M1 = Mg, Zn, Zr, B, Hg, Si, Sn, Ge

M2 = transition metal
Generally speaking, transmetallation involves replacing the halide or pseudohalide in a transition
metal (M2) complex with the organic group of a "main group" organometallic (M1) reagent. This step
is almost always the rate-limiting step and is usually the culpret when cross-coupling reactions fail.
This is an equilibrium, so to ensure success both partners must gain some thermodynamic benefit. Often
this can be enhanced by appropriate "activation" of the main group element.
Isomeric integrity (cis, trans) is usually maintained when R is an olefin. With alkyl metals the situation
is more complicated. With polar solvents, alkylstannanes can transmetallate with inversion of
configuration (open transition state?), but in less polar solvents retention is seen (closed transition
state?). However, aliphatic organoboron reagents tend to proeed with retention.
R

R
L

Pd

L
C

SnBu3

Pd

SnBu3

L
X

proposed open t.s.

leading to inversion

similar mechanisms could be drawn

with other metals under apprpriate
activation

proposed open t.s.

leading to retention

Electrophilic Attack on Coordinated Ligands

Several different reactivity modes depending on the metal, ligand, and electrophile involved. More
specific examples will be discussed as needed.
Electrophilic cleavage of -alkyl metal bonds Note metal is removed.
R

E+

Fe(CO)2Cp

Me

M+

retention at R

DCl

Me

CpFe(CO)2Cl

Attack at -position Forms carbenes

Ph
M CHPh +
Ph3C+
H

M C

Ph
M C

TfO

TMSOTf
OC
OC

Fe

CH2OH

M C

H+

CH2Cl2
90 C

OC
OC

Fe

+
CH2

Me3SiOH

Electrophilic Attack on Coordinated Ligands

Several different reactivity modes depending on the metal, ligand, and electrophile involved. More
specific examples will be discussed as needed.
Attack at -position
M

+ Ph3C+

E+

M
R

E+

M C
E

vinylidene

MeOTf
OC

Mn

OC

Mn

Me

OC

OC

CO2Me

CO2Me
O

OMe

Me3OBF4
(OC)5W

(OC)5W

Ph

(OC)5W

Ph

Ph

Electrophilic Attack on Coordinated Ligands

Several different reactivity modes depending on the metal, ligand, and electrophile involved. More
specific examples will be discussed as needed.
Attack at -position
M

+ E+

R2
R1

+ R3CHO

SnBu3

R2

OH

PdCl2(PPh3)2
R3

likely involves formation of

1-allyl

R1

intermediate

B
A
Cp(CO)3Mo

Cp(CO)3Mo

ArSO2NCO
Me

Me

N
O

SO2Ar