5.

44 An Introduction to Organometallic Chemistry

Professor Stephen L. Buchwald (18-490, sbuchwal@mit.edu)
Grader: Phill Milner (pjmilner@mit.edu)
!
Classes: 3/31, 4/7, 4/14, 4/15, 4/28, 5/5, !
Hour Exam: April 28 in class (1.25 hours)-25% of grade!
Presentation: May 5--25% of grade.!
Final Exam: May 12, in class--50% of grade!
There is no required textbook for this class.
Note: Much of the handout and lecture material is taken, with
permission, from Organometallic Chemistry and its Application
to Organic Synthesis, a course given by E.N. Jacobsen (Harvard)
and S.L. Buchwald (MIT). It is for your personal use. Please do
not reproduce or distribute this material.
S.L. Buchwald and E.N. Jacobsen, 2005-12, All rights reserved.

Representative Text Books

Hartwig, Organotransition Metal Chemistry

Crabtree, The Organometallic Chemistry of the Transition Metals
Elsenbroich, Organometallics
Spessard, Miessler, Organometallic Chemistry

Organotransition Metal Chemistry

FEATURES:
Stabilization/Synthetic Utilization of Reactive Organic Structures
H2C
ZrCp2

CH2

H2C

Co

Fe(CO)3

Activation of Normally Unreactive Molecules

+
Me

CHO

(CO)8Co2

CO/H2

CHO
+

Me

Me

Me

Changes From Substrate-Controlled Outcome of Reactions

F3C

F3C
OTBS
N
BOC

F3C

H2/Pd-C
(w/desilylation)

F3C

OH

OH

N
BOC
99:1
78%

N
BOC
Cy3P
Ir
N

PF6

Crabtree's Catalyst

Crabtree

OH
N
BOC

158:1
91%

Features of Organotransition Metal Chemistry

Extraordinary C-C Bond Constructions (relative to traditional organic chemistry)

Cl
Kumada Coupling

CH3

Ni(PPh3)2Cl2

+ MeMgBr

R'

I
Larock Indole Synthesis
(first step is a Heck reaction)

N
R

O
Ring Closing Metathesis

Me

R'

R"

5% Pd(OAc)2/Ph3P
N
R

Ph

Mo(CHt-Bu)(NAr)[OCMe(CF3)2]2

C2H4

R"

Ph

Me
Me O

Me O
Alkyne Cyclotrimerization

TMS

CpCo(CO)2

TMS
H
TMS

TMS

Asymmetric Catalysis
Commercial Preparation of Menthol
Me

Me

Me

(S)-BINAP-Rh(I)

Me

NEt2

Me

Me
NEt2

Me
Me
PPh2
PPh2

Me

CHO

OH
Me

(S)-BINAP

Me

Me

()-menthol

Commercial Preparation of Aspartame

CO2H
NHCOCH3

(R,R)-PNNP-Rh(I)

+ H2

CO2H

NHCOCH3

Ph

Me
N

(R,R)-PNNP =
N
Ph

CO2H

PPh2

NH2

PPh2
HN
Me

aspartame
CO2H

What is Organometallic Chemistry?

Chemistry of complexes containing transition metal-carbon bonds (Narrowest Definition)

C
M

alkyl

carbene
(alkylidene)

alkynyl

alkenyl

carbyne
(alkylidyne)

Complexes that do chemistry involving intermediates containing transition metal-carbon bonds (Broader
Definition -- Most Widely Accepted). This definition encompasses many of the catalytic processes that we are
interested in.
(Ph3P)3RhCl (Wilkinson's catalyst-olefin hydrogenation and isomerization)
Pd(PPh3)4 (Cross-couping and Heck Chemistry) PdCl2/CuCl2 (Wacker catalyst)
Rh2(OAc)4 (Carbenoid Insertion Chemistry)

Any M-C Bond Containing Species, where M is more electropositive than carbon (Broadest Definition -Applied by Organometallics)

SiR4

PR3

SnR4

AlR3

Transition Metals

Li

Be

Na

Mg

Ca

Sc

Ti

Rb

Sr

Zr

Cs

Ba

La*

Hf

11

12

Al

Si

Co

Ni

Cu

Zn

Ga

Ge

Ru

Rh

Pd

Ag

Cd

In

Sn

Os

Ir

Pt

Au

Hg

Tl

Pb

Cr

Mn

Fe

Nb

Mo

Tc

Ta

Re

LATE

Transition Metal = Metal that can have a partially filled d shell

NOTE:
in free metal 4s below 3d
in complexes 3d below 4s

14

10

EARLY

13

e.g. Fe metal is 4s23d6

but Fe(CO)5 is 3d8

The d Orbitals
z
y
x

dx2y2

dz2

dxz

dxy

Two orbitals with lobes on the axes

and three orbitals with lobes between the axes
Lobes oriented at 90
Centrosymmetric

dyz

Bonding in Organotransition Metal Complexes

bonding

Covalent (may be more or less polarized):

MH

CH

Malkyl

CC

vis

MCl

CCl

MOR

COR

Dative:
M

:CO

:PR3

vis F3B

:OEt2

 bonding

Covalent (again, may be more or less polarized):

M

vis

CR2

R2C

CR2

Dative, metal as acceptor:

M
M

Cl

halides, alkoxides, amides

are donors

Cl

Dative, ligand as acceptor:

M
M

CO

CO

bonding

CO, for example,

is a acceptor
( acid)

Bonding Representations

CO

H2C
H2C

CH2

Co

OC

Fe

Cl
CO
CO

Fe(CO)3

Pd

Ph3P

PPh3
Cl

CO

Lines do not necessarily symbolize shared electron pairs:

- All connections (covalent, dative) are symbolized by a simple line
- Formal charges not shown
- 2 or more bonding represented by a single line
aimed toward the center of the array

Lone pairs on metal not shown

Oxidation states usually not shown

A Primer on MO Theory

Ionization Potential

The MO description of a covalent bond can be represented simply as:

M X

Where the bond energy is related to E, and:

Small difference in electronegativity (M X small)

stronger covalent bonds

orbital overlap
M X

Larger differences in electronegativity (M X large)

weaker covalent interaction
stronger ionic interaction

Electronegativity

H
2.2

Li
1.0

16

17

N
3.0

O
3.4

F
4.0

Si
1.9

P
2.2

S
2.6

Cl
3.1

Ga
1.8

Ge
2.0

As
2.2

Se
2.5

Br
2.9

Cd
1.7

In
1.6

Sn
1.8

Sb
2.0

Te
2.1

I
2.6

Hg
2.0

Tl
1.6

Pb
1.9

Bi
2.0

Po
2.0

At
2.2

13

14

Be
1.6

B
2.0

C
2.5

Na
0.9

Mg
1.3

Al
1.6

K
0.8

Ca
1.0

Sc
1.3

Ti
1.5

V
1.6

Cr
1.6

Mn
1.6

Fe
1.8

Co
1.9

Ni
1.9

Cu
1.9

Zn
1.7

Rb
0.8

Sr
1.0

Y
1.2

Zr
1.3

Nb
1.6

Mo
2.1

Tc
1.9

Ru
2.2

Rh
2.3

Pd
2.2

Ag
1.9

Cs
0.8

Ba
0.9

La*
1.1

Hf
1.3

Ta
1.5

W
2.3

Re
1.9

Os
2.2

Ir
2.2

Pt
2.3

Au
2.5

10

11

12

15

Lanthanoids and Actinoids: 1.1 1.3

Pauling The Nature of the Chemical Bond, 3rd. Ed.; 1960
Allred J. Inorg. Nucl. Chem. 1961, 17, 215

Electronegativity
Covalent bonds in late organotransition
metal complexes are relatively non-polar
Some important trends:

Early metals

Main Group

Transition metals

Late metals

More covalent bonds

More metallic (more electropositive)

Weaker bonds to carbon
LESS metallic (more electronegative)
STRONGER bonds to carbon

Descriptive Periodic Table

M+ XGroup
element
Pauling EN

Sc

cost

$$$$$

More Ionic

Ti
1.3

1.5

$
Zr

$$
Nb

$$
Hf

cost:

$
$$
$$$
$$$$
$$$$$

Very cheap
cheap
moderate
expensive
very expensive

$
Mo

$$
Ta

$$

$
Tc

$$$
W

$$$

$
Ru

$$$$$
Re

$$$$

$
Rh

$$$$
Os

1.9

$
Pd
2.3

$$$$$
Ir
2.2

$$$$$

Ni
1.9

2.2

1.9

10

Co
1.8

1.9

2.3

Fe
1.6

2.1

1.5

Mn
1.6

1.6

1.3

Cr
1.6

1.3

$$$

M-X

More Covalent

2.2

$$$$
Pt
2.2

$$$$$

2.3

$$$$$

Periodic Trends in Bonding

More ionic
More oxophilic

M+ X

Ti

Most
electropositive

Cr

Mn

Fe

MX

Co

Ni

Zr

Nb

Mo

Tc

Ru

Rh

Pd

Hf

Ta

Re

Os

Ir

Pt

Stronger
bonds

Most
electronegative

All Hydrides Are Not Created Equal

hydridic
Cp2Zr

H
Cl

Schwartz's
Reagent
acidic

(CO)4CoH

Catalyst for
oxo process

Cp2Zr

Cl

pKa < 1 in H2O

8.4 in CH3CN

Kinetic and Thermodynamic Acidity of M-H Complexes:

Norton JACS 1987, 109, 3945.

M-C Bond Energies in Organotransition Metal Complexes

abnormally weak in this case

D(H-X) in kcal/mol

120

110

100 neopentyl

Ph
(CH3) > 1 > 2 > 3

Me

Vy

M-C correlates with H-C

sp > sp2 > sp3

Pentyl

Cy

90
40

50

60

70

80

90

D(Ir-X) in kcal/mol

In general, if an equilibration mechanism exists (and it does), alkyl groups will isomerize to 1 product.
suggested
as due to
steric
hinderance

M
M

Bergman Polyhedron 1988, 7, 1429

Neutral Dative Ligands

ML

:L

(or ML+)

MCO

:C O

(or MCO+)

MPR3

:PR3

(or MP+R3)

M
:L

M
M

or

+
+

 Backbonding
:PR3

:CO

R2C

CR2

Relatively weak donors (Lewis bases)

can be excellent ligands for transition metal complexes

C
M

CO

M
C

d
CO as donor

C
C

CO as acid

alkene as donor

d
*
alkene as acid

Dewar-Chatt-Duncanson model

NOTE: CO and olefins do not form stable complexes with d0 TMs

-Backbonding

Spectroscopic evidence:
More backbonding
M

CO

(cm1)

2143

H3BCO
2164

Ni(CO)4

2060

Weaker CO

Co(CO)4
1890

Fe(CO)42
1730

Mn(CO)43
1670

pKa (in acetonitrile)

Chemical evidence:
HCo(CO)4

8.4

HCo(CO)3PPh3

15.4

Reflects stability of Co(CO)4 vs. Co(CO)3PPh3

Cr(CO)44
1500

Olefin Complexes vs. Metallacyclopropanes

C

C
C

M
C
alkene as donor

d
*
alkene as acid
If M is electron donating, backbonding is strong:

If M is electron withdrawing, backbonding is weak:

Zr(+2) has 2 d electrons

(and Zr is more stable in higher OS)

Zr(+4) has no d electrons

Cp2(Me)Zr+

Complex is unstable

Cp2Zr

Cp2Zr

Olefin rendered electrophilic

Complex is stable
Olefin rendered nucleophilic

The more electron-rich the metal, the more -backbonding is seen. More
metallacyclopropane character.
1

*Cp

1.337
Ti

1.536

C-C bond length 1.438

*Cp
nC4H9

ZrCp2
PMe3

nC4H9

nC4H9
ZrCp2
PMe3

180

135.8

nC4H9
120

1.286

1.20
metallacyclopropene-much closer

1.34

Phosphines
M

PR3

PR3 as donor
But very electron deficient phosphines can be excellent ligands for TM's
(e.g. PCl3, P(OR)3, etc.)

2.24
Ph2
P
Cl
Pt
P
Cl
(CF3)2

Structural evidence for phosphine as acceptor:

P
d

2.37

2.17

Popular, but almost certainly incorrect interpretation:

M

2.32

R
R
R

d
R

More likely interpretation:

R
R

*
Orpen Chem. Comm. 1985, 1310

Cone Angle

R
R

R
P

2.28

Ph2P

104

P(OMe)3

107

PMe3

118

PPhMe2

122

PPh2

125

PEt3, PPh2Me

132

PPh3

145

PCy3

170

P(t-Bu)3

182

P(o-tol)3

194

PCy2

SPhos

240*

iPr

XPhos

256*

PCy2
MeO

iPr

PF3

OMe

Cone angles for nonphosphine ligands:

75

Me

90

CO

95

Cp

136

Tollman Chem. Rev. 1977, 77, 313

iPr

*For a different view-"% Buried Volume: Nolan Chem. Commun. 2010, 46, 841

Electron Counting
Method 1: The Dative Ligand Formalism
Assume all ligands are bound datively:
MCO
M
:CO
MCl

M+

:Cl

MCH3

M+

:CH3

MH

M+

:H

M=O

M+2

::O2

1. Disconnect all ligands according to the dative ligand formalism

2. Place charges of the complex (if any) on the metal
3. Count electrons remaining on the metal (gives d electron count)
4. Add to electrons donated by the ligands
ADVANTAGE: Gives d electron count (and hence OS) directly

Common Ligands
X-

(-1

c h arge)

2 e-

1
-allyl

Cl-, Br-, I-, R- (e.g., CH3-), H-, Ar-

-1

-1

-1

RO-, RS-, R2N- (if no -bonding--see later)

2 e-

B: (Lewis Bases-neutral)

-allyl

:CO
C a r b on monoxide is probably the most important ligand in terms of
industrial applications.
R3P :

cyclopentadienyl (Cp)

C h a n g i n g R can radically alter properties, e.g.,

M e3P:, small, basic, volatile liquid (b.p. ~35 C), very foul odor
P h3P:, much larger, decreased basicity, white solid (m.p. 79-81 C)
M e3P is a far superior donor of electron density to metals than is Ph3P

-systems

neutral

-2

Me

Me

Me
Me Me

alkynes

neutral

-2

By placing substituents on the Cp ring, the properties of analogous complexes can be

dramatically altered. The most common is the pentamethylcyclopentadienyl ligand
usually denoted as Cp*.

olefins

Me

Me

Me

The Cp* ligand has several effects. First, it

is significantly more electron donating
Me than the Cp ligand. It is also of much
greater steric bulk. One manifestation of
this added size, is the tendency for
complexes to be monomeric and, hence,
often significantly more reactive.

Me

M
M
neutral

1,3-dienes
neutral

4
O

M
bridging carbon monoxide

neutral

OR

RO

-1, 2 e-

OR

RO

-1, 4 e-

OR

RO

-1, 6 e-

Here -bonding puts more electron

density onto the metal.
Note: an RO- group is isolectronic with
a cyclopentadienyl group.

-1 for each
metal

2 for each
metal
M

metal-metal bond

neutral

1 for each
metal

metal carbene

neutral

CH2

CH2

metal alkylidene

-2

CO

Example:

OC
OC

Step 1:

Mn+

Mn
CO

H
Mn0 is d7
so Mn+ is d6
(6 unshared electrons)

Step 3:

:CO
OC:

CO

:CO
:H

OC:
:CO
Step 2: N/A

Step 4:

MnI (d6)
H
5 x CO

6
2
10

18 e
(coordinatively saturated
complex)

CO

Example:

OC
OC

Step 1:

:CO
OC:

Mn

:CO

CO

Mn
CO

Step 3: Mn0 is in the 7 th column,

no charge
so metal e count = 7

OC:
:CO
Step 2: N/A

Step 4:

Mn
H
5 x CO

7
1
10
18 e
(same answer)

Electron Counting Examples

(Using Dative Ligand Formalism)
Pd(PPh3)4 ("tetrakis")
Ph3P:

:PPh3

RhCl(PPh3)3 ("Wilkinson's catalyst")

Ph3P:

Pd0
Ph3P:

Pd0 d10
4 x PPh3

:PPh3
Rh+

:PPh3

10
8
18 e

:Cl

Ph3P:

RhI d8
3 x PPh3

Cl

6
16 e

Electron Counting Examples

(Using Dative Ligand Formalism)

[Rh(COD)2]+ ("Schrock-Osborn complex")

VO(acac)2 (an epoxidation catalyst)

O

Rh+

O
O

O2
::

O
O

V++++
acac

RhI d8
2 x COD

8
8
16

:O:

For electron-counting purposes,

charge on the complex is almost always
assumed to reside on the metal

acac

acac:
4 e, 1 charge

VIV d1

2 x acac

8
4

oxo

13 e
The 18 e "rule" often fails for early TM's

"Non-Innocent" Ligands
Hapticity
3-allyl

CH2
M

CH2
4 electron donor
(1) charge

1-allyl
M

M
C
H2

2 electron donor
(1) charge

[(PMe3)2Pd(allyl)]+

Me3P
Me3P

Me3P

Pd+

Me3P

Me3P:

H2

Me3P:

H2

Me3P:

:C

Pd2+

Pd+

:C

Pd2+
Me3P:

PdII d8
2 x PMe3

8
4

PdII d8
2 x PMe3

8
4

1-allyl

3-allyl

14 e

Predict 3-allyl complex to be more stable. IT IS.

16 e

Basic Reaction Types

LnM(a) + X-Y

1.!Oxidative-Addition

X
LnM(a+2)
Y

Note there is an increase in formal oxidation state (+2) of the metal.

Example:

Br

(Ph3P)2Pd

Br

Pd

PPh3

Ph3P

This is the most important means to make carbon-metal bonds.

X
LnM(a+2)

2.!Reductive-Elimination

LnM(a)

X-Y

Y
Note there is a decrease in formal oxidation state (-2) of the metal.
Example:
TMS

Ph3P
Pd

Ph3P

(Ph3P)2Pd

TMS
This is the most important means to form carbon-carbon bonds.
Review: Hartwig Inorg. Chem. 2007, 46, 1936

Basic Reaction Types-2

3. 4-Centered Reactions
(-bond metathesis)

L nM(a) A + X-Y

t-Bu

Br H
Br 2

Cp2Zr

L nM a

L nM(a) X + A-Y

t-Bu
H

Br

Cp2Zr

Cl

Cl

t-Bu

H
Br

Schwartz JACS 1975, 97, 3851

review: Waterman OM 2013, 32, 7249

This is an important path for d0 (e.g., Zr(IV) ) metals to get substrates on and off the metal.
4. Ligand Substitution
A) Simple Exchange-can be either associative or dissociative
L nM
tBu3P

L n-1M

A (neutral, 2e- donor)

CO2Me

Cl

tBu3P

Cl

Example:
Stille ACIEE, 1986, 25, 508

tBu3P

Cl
Pd

MeO 2C

tBu3P

B) Transmetallation

Pd

Pd

L nM

X +

Ph
PPh 3

Pd

M'R

PPh 3
Br

e.g., CH 3Li

L nM

M'-X

or nBu 3Sn

Ph
+

Note there is
no change in
formal
oxidation state
of the metal.

nBu 3Sn

PPh 3
nBu 3SnBr

Pd

PPh 3

Basic Reaction Types-3

forward:
insertion of
olefins and
alkynes into M-H
and M-R'

5.!Migratory Insertion Processes

A) Small molecule insertions
O
carbon monoxide
"insertions"

C
LnM

LnM

LnM

LnM

This is the primary means by which small molecules (e.g., CO, alkenes, alkynes) are
incorporated into metal complexes and subsequently into organic products.
AcN(H)
Br

CO/H2O
L
L= Ph3P

Pd
L

CO

Br

reverse: For R=
H, -hydride
elimination
reactions
CHNF, Ch 6

L
cf. Tsuji, Palladium Reagents and
Catalysts

Pd
L
O

AcN(H)

CO
Ph3P Rh
Ph3P
H

CH3

Ph3P Rh CO
Ph3P

Stille Comp. Org. Syn.,

Vol 4, Ch 4.5, p 913

CH3

B) Oxidative-Cyclization Processes
ox state of M
a

insertion

ox state of M L M
n
a+2

LnM

ox state of
M a+2

LnM

This process is termed oxidative cyclization since two organic groups are coupled together and the metal is formally oxidized.

Cp2Zr

TMS

TMS

TMS

insertion
NBn

Cp2Zr

NBn

Cp2Zr

NBn

Negishi J. Am. Chem. Soc. 1989, 111, 3336

Basic Reaction Types-4

6.![2+2] Reactions
LnM

CH2
R

LnM

LnM

OR'
LnM

CH2

H2C
OR'

OR'

LnM

LnM

Bn

Bn
N

MLn

H2C

R
R'
Petasis, JACS 1990, 112, 6392
Grubbs, Pine Comp. Org. Syn., Vol 5, Ch 9.3, p 1115

R'

Bn
Example:

R
R'

Grubbs, Miller, Fu Acc. Chem. Res. 1995, 25,

446-452, Grubbs Tetrahedron 1998, 54, 4413

MLn
CH3

CH3

H3C

7.!Activation of LigandsToward Attack by External Nucleophiles

LnM+

Nuc-

Nuc

Nuc

LnM

+
MLn

MLn

Nuc

X
LnM +

Nuc-

LnM+
X-

Nuc-

LnM +

Hegedus Comp. Org. Syn., Vol 4, Ch 3.1, p 551

Tsuji Palladium Reagents and Catalysts, Wiley, 1995

Basic Reaction Types-5

PF 6

Cl

CpRu

PF 6
CpRu

OMe
OH

HO

TBSO
TBSO
EtO
O

O
N
H

H
N

88%

N(H)Boc

EtO

N
H

OMe
OH

O
H
N

N(H)Boc
O
Pearson TL 2005, 46, 3966

8. Additional Elimination/Abstraction Processes

R
a) -elimination Reaction

L nM

L nM
H

tBu
Me3Si
Me3Si

Mo

Me3Si

SiMe3

Me3Si

tBu

M
P

CH 3
OAr

M= Hf, Zr

SiMe3

Schrock JACS 1997, 119, 11876

L nM
H

R'
CH 3

Mo

b) -abstraction Reaction

h
N

L nM

iPr 2P

CH2

full ligand is:

M
P

OAr

Schrock Acc. Chem. Res. 1979, 12, 98

R'H
PiPr 2
N

Mindiola ACIE 2014, 53, 10913

Basic Reaction Types-6

We've already seen the -hydride elimination reaction:

R
LnM
R'

R Reductive
Elimination

-hydride
elimination
LnM

LnM

R'

R
R'H

A related transformation is the -abstraction reaction:

R
LnM
R'

-abstraction

LnM

R'H

This process is a concerted process which accomplishes the same overall transformation. This can be important
in cases in which -hydride elimination would lead to an unstable intermediate.

Cp2Zr

Cp2Zr
CH4

H
Me

d0

Cp2Zr
Me

Cp2Zr

Cp2Zr

CH4

Buchwald Science 1993, 261, 1696

Oxidative-Addition--Summary of Key Features

X
LnM(a)

LnM(a+2)

X-Y

!The reaction proceeds with a net increase in formal oxidation state of the metal center.
Favored in electronic rich (e.g., low valent) complexes.
Electron donating ligands (e.g., trialkylphosphines) increase the facility of oxidative addition.
Disfavored in electron deficient (e.g., high valent or cationic) complexes.
Electron withdrawing ligands (e.g., CO) decrease the facility of oxidative addition reactions.
!The reactions are, in principle, reversible via reductive-elimination pathways.
!Often ligand dissociation is required:

LnM

18 e- complex
(Often unreactive)

L4M 18 e- complex
(e.g, M= Pd)

-L
-nL

Ln-1M
L2M or L1M

16 e- complex
14 or 12 e- complex

Hartwig J. Am. Chem. Soc. 1995, 117, 5373

!Oxidative-Addition is a generic descriptor providing no mechanistic information. Many mechanistic pathways fall
under this term, including SN2, radical, 3-centered, ionic and bimetallic processes.
Crabtree, Ch 6, CHNF, Ch 5, Stille Review

Oxidative-Addition Summary of Key Features

SN2-like
Displacements-sp3
hybridized carbon:

R
LnM

LnM

LnM
X

R Evidence for cationic intermediate:

Puddephatt Organometallics 1987,
6, 2548

OC
Ph3P

Ir

PPh3

CH3

Ph3P
Cl

Cl

Stereochemical
Evidence:

Ir

CO
PPh3

Ph3P
Cl

(Ph3P)4Pd

Ph

(S)
Cl

CO
PPh3

CH3

CH3

H D

Ir

trans product

Cl

inversion

PPh3

PPh3
Pd
Ph
(R)
D H

Ph

RX: simple alkyls primary > secondary (mostly radical) >>> tertiary (radical)
Until recently, not very synthetically useful--often see radical and reduction products.
Pearson JACS 1982, 102,
1541

X: I- > RSO3- ~ Br- > Cl-!!RSO3- best to minimize radical

Other useful substrates (mechanistically
ambiguous in many instances):

X Ar

OR X

CHNF, Ch 5; Stille, Review;

ACIEE 1986, 25, 508

OH

Oxidative-Addition Summary of Key Features

Concerted 3-Centered Rxs-common for H2, R3SiH, reagents where groups are together (e.g., alkenes, alkynes)

LnM

X-Y

LnM

LnM
Y

LnM

R
LnM

LnM
R

H
CO

Ph3P
"Vaska's Complex"

PPh3

Ph3P

MLn

Ir
Cl

PPh3

OC

Ir
Cl

rel rate: I > Br > Cl (>100 : 14.3 : 0.93)

H
H
MO analysis

M
H
H

d
L

Stable dihydrogen complexes first isolated in 1984:

W(CO)3(iPr3P)2 + H2

Kubas JACS 1984,106, 451

OC

CO
H

OC

0.84

free H2 0.74

Oxidative Addition-Radical Mechanisms

Radical Reactions: Both chain (most common) and cage seen:
X

LnM

LnM-X

R
LnM

X
-L
L3Pt

L4Pt

16e-

Br

e- transfer

L
Br
L3Pt

Br

Pt
Br

Pt

L
Stille, Review,CHNF, Ch 5, Crabtree, Ch 6

Br
Ph3P

CO
+ CH3CH2-Br

Ir
Cl

Ph3P
Cl

PPh3

Ir

CO
PPh3

CH2CH3
via: CH3CH2 + IrCl(CO)L2

Note change in mechanism!

from SN2 to radical upon!
change from MeI to EtBr!
as substrate.
Evidence:

RIrII Cl(CO)L2 + RX

RIrII Cl(CO)L2
R(X)IrIIICl(CO)L2 + R

Observation of an induction period

Promotion by radical initiators
Observation of homocoupling products
Loss of stereochemistry with chiral electrophiles

Oxidative-Addition--Summary of Key Features-3

Fairly recently Fu and subsequently Beller have shown that primary alkyl bromides and chlorides with hydrogens are viable substrates in Suzuki and Kumada type coupling processes, for example:

[(Cy3P)2Pd]
Me

(Cy3P)2Pd

Br(Cl)

Me
8

Br(Cl)

Fu JACS 2001, 123, 10099, ACIEE 2002, 41, 1945

Beller ACIE 2002, 41, 4056

Ph

Ph

Br

(tBu2(Me)P)2Pd
0 C/Et2O

tBu
Me

tBu

Pd

Me
tBu

Br tBu

Fu JACS 2002, 124, 13662

Oxidative Addition of Alkyl Bromides to L2Pd(0)

R
R Br

Entry
1
2

R Br
Br

Me

Me

Br

L Pd

G [kcal/mol]

1.0

19.5

0.19

20.3

Br

Me

Me

Br

0.054

21.0

<0.0001

>24.0

Me

Entry

G [kcal/mol]

P(t-Bu)2Me

19.5 (0 oC)

PCy3

20.0 (0 oC)

P(t-Bu)2Et

25.4 (60 oC)

P(t-Bu)3

>28.4 (60 oC)

L Pd
Br

THF, 0 oC
L = P(t-Bu)2Me

krel

Me
Me

Me

Me
P

P
Pd

Pd

Me

Me
Favored
conformer
much more
hindered at Pd

similar steric environments for the

approach of R-X to Pd

Pd

Very sensitive to steric effects

Fu Angew. Chem. Int. Ed. 2003, 42, 5749

Oxidative-Addition--Summary of Key Features-4

Oxidative-Addition at sp2 carbon: From the perspective of synthesis, this is the most important aspect of ox-add.
Of these, most important systems are Ni(0) and especially Pd(0).
L
LnM

+ R

M X

LnM

M X
R

For ArX: Pd: Pd(PPh3)4 X= I > Br > OTf >> Cl (requires electron withdrawing subs--however, more modern
systems allow for this to occur under reasonable conditions), however OTf > Br for PdCl2(PPh3)2 (Catalyst
better able to coordinate to oxygen of triflate).

Stille JACS 1987, 109, 5478

Ni: X= I > Br> Cl > CN >> F! Cl is the most synthetically useful.

Mechanistically, with Ni complexes, this is a very complex reaction.
CHNF, Ch 5, Tsuji Palladium Reagents and Catalysts, Wiley, 1995
Kumada P& A Chem. 1980, 52, 669; Stille ACIEE 1986, 25, 508;JACS 1984, 106, 4630

Possible Mechanisms:

LnM +

electron
transfer
ArX

nucleophilic
aromatic
substitution

LnM

ArX

LnMX Ar

MLn
X

concerted
For LnNi + ArX: the top pathway is usually followed (electron transfer)
For LnPd + ArI: the bottom pathway is followed

LnM(Ar)X
MLn
X

Oxidative-Addition--Key Features-5
Examining the reaction of (PPh3)4Pd + ArI:
(PPh3)4Pd

(PPh3)3Pd + PPh3

Keq >> 1

(PPh3)3Pd

(PPh3)2Pd + PPh3

Keq << 1

(PPh3)2Pd + ArI

(PPh3)2Pd(Ar)I

rate= kexp [ArI] [Pd(0)]/[PPh3]; rate is inversely proportional to [PPh3].

Hammett plot--= 2.3; electron donating substitutents on aryl halide slow rate.

For reactions of

H is the same in toluene or THF. This indicates that there is no solvent coordination involved in the
oxidative addition step. It is most consistent with a mechanism in which there is "no charge development in
the transition state," i.e. the concerted pathway.
Kochi has previously shown that there are large variations (a factor of ~9) in the rates of oxidative addition of
LnNi(0) to ArX with a change in solvent polarity. This is a reaction which is believed to proceed via the electron
transfer pathway.
Amatore calculates that electron transfer from L2Pd to ArX is "more endergonic than from LnNi(0) to the
same halide" by 35 kJ/mol (8.4 kcal/mol).
Amatore Organometallics, 1990, 9, 2276

Oxidative-Addition--Vinylic Substrates
Alkenyl Halides and Triflates: Pd: I, OTf, Br commonly employed. Recent work indicates that Cl is viable: Ni:
Cl and Br most studied, I also works.
Mechanistic Issues:
1)!Reactions proceed with retention of double bond geometry; inconsistent with free radical mechanisms.
2)!Ni(0) > Pd (0) > Pt (0), but Pd by far the most synthetically useful. Use of nickel catalysts can often lead to
radical products.
3)!Reactions of vinyl bromides are faster than reactions with CH3I.

Postulated Mechanism:
X

Precomplexation

R''

X
LnM

X
R''

LnM

R''

LnM
R

R'

R'

R'

Transformations of vinyl chlorides involving oxidative addition: Fu JACS, 2000, 122, 4020
Stille, Review; CHNF, Ch 5; Stille ACIEE 1986, 25, 508

Stepwise Transformation
Br
Br
Br
Ar

PdL2

PdL2

PdL2

<30 C

Ar

Ar

observed by NMR stable

below 40 C
(Corresponding I not observable)

L2= DPPF =

CH3MgX

Fe

PPh2
PPh2

Me
PdL2

Me
PdL2

Ar

Me

Ar
"L2Pd"

Ar
stable below 20 C

observable at < 0 C
Brown Inorg. Chem. Acta. 1994, 220, 249

Reductive-Elimination Summary
X
LnM(a)

LnM(a+2)

X-Y

Y
!!Cis orientation of X and Y is required.
!!Relatively favorable for electron deficient complexes. Relatively disfavored for electron !rich complexes;
reductive-elimination leads to a complex in which the metal has a !reduced formal oxidation state.
!!Rate enhanced by bulky ligands; reductive-elimination leads to a complex with decreased coordination number.
!!Reductive elimination from a coordinatively saturated intermediate is favored as is formation of an
electronically stable product (i.e., reaction to form an unstable molecule is disfavored).
!!Reductive elimination has been shown to proceed with retention of !configuration at carbon.
Ph3P

Pd

CH3

Ph3P

PPh3
Ph

(R) D

HD

O
OTBS

PPh3

Ph

CH3

Ph

H3C

H D
L2Pd

Pd

(Ph3P)2Pd

H
CHNF, Ch 5,Stille, Review

H D
HD

OTBS

L2Pd

L2= DPPF

O
Review: Hartwig Inorg. Chem. 2007, 46, 1936

Woerpel JOC 1998, 63, 458

Rates of Reductive Eliminations: Bite Angle Dependence

P
bite angle

Pd

Pd
P

R'

P2Pd

R R'

R'

P
larger

Angle increases in the transition state for reductive elimination

Larger bite angle, faster rate of reductive elimination
Ph2
P

bite angle = 89
Ph
Pd

P
Ph2

(DPPP)Pd

Me

1/2=30 min @ 35 C

Me

bite angle = 97
Ph2
P

Ph
(DPPF)Pd

Pd

Fe
P
Ph2

Me

1/2~15 min @ 0 C

Me

Consistent with DPPF's efficacy in cross-coupling reactions.

Brown Inorg. Chim. Acta. 1994, 220, 249
review on bite angle effects: Dierkes, van Leeuwen, J. Chem. Soc. Dalton 1999, 1519

Electronic Effects on Reductive Elimination from Pd(II) Complexes

Ph2
P Ar
Pd
P R
Ph2

t-Bu

DPPBz
Ar R

40-100 C

krel

Me

>600

CH2Ph

>250

CH2C(O)Ph

31

CH2CF3

1.7

CH2CN

CF3

no rxn

Ar =

More electron rich alkyl groups reductively eliminate more rapidly.

Hartwig Inorg. Chem. 2007, 46, 1936

Electronic Effects on Reductive Elimination from Pd(II) Complexes

Ph
Ar3P

Me
Pt

Ar3P

Ph

Ar3P

Ph

CH4

Pt

Ar3P
Ph
Ar

kobs

(x104)

C6H4Cl

9.2

C6H5

4.5

C6H4Me

1.4

C6H4OMe

0.47

More electron donating the ligands

are, the more slowly the rate of
reductive elimination occurs. This is
consistent in the lowering of energy of
a transition state that is more electron
rich than the ground state of the starting
material.

reaction rate unaffected by addition of Ar3P. Therefore, reaction doesn't proceed by either an associative
or a dissociative pathway.
reaction shown to be intramolecular by crossover experiments.
Ar3P
Ar3P

Pt

CH3
H

Ar3P
Ar3P

Pt

CD3
D

Ph
Ph

Ph

Ar3P

CH4

Pt

Ar3P

+ CD4

Ph
very little CH3D or CD3H was seen
Halpern JACS 1978, 100, 2915

Relative Rates of Reductive Elimination

R
>

M
H

R
>

M
R

R
M
R
b2

hybrid orbital

1b2
1a1

a1

note: sp3 orbitals must

rotate toward each other
to reach transition state.

b2

M
H
1b2
1a1

spherical symmetry of s orbitals

makes red-elimin easier-better
overlap in transition state

a1

See: Albright, Burdett!

and Whangbo:!
Orbital Interactions in!
Chemistry, pp 372-380.

Electronic Effects on Reductive Elimination from Pd(II) Complexes

Ph2
P

Ph

85 C

Pd

Fe

1.5 h, 90%

N(tolyl)2

P
Ph2
Ph2
P

Ph

25 C

Pd

Fe

1.5 h, 80%

N(H)Ph

P
Ph2
Ph2
P

Ph

0 C

Pd

Fe
P
Ph2

N
H

Me

1.5 h, 64%

PhPN(tolyl)2

(pKa of HNPh2 = 25)

HNPh2

(pKa of H2NPh = 30)

PhN(H)(i-Bu)

(pKa of H2Ni-Bu ~ 41)

Me

More electron-rich N reductively eliminates faster

Hartwig Inorg. Chem. 2007, 46, 1936

Electronic Effects on Reductive Elimination from Pd(II) Complexes

Ar
L2Pd

Ar Nuc

L2Pd
Nuc
C P

Relative Rates:
>

>

C S

>

C N

C O

Ar

Ar

L1Pd

L2Pd

>
Nuc

Ar Nuc

Nuc

L1Pd

Ar Nuc

L2Pd

Implies that reductive elimination from Pd(II) complexes faster with monodentate than with chelating ligands.
X
reductive elimination
LPd

Ar NR2

L2Pd

NR2
-hydride elimination

Favored by: 1. X= EWG

2. More electron rich R
3. Larger ligands

Ar H
Hartwig JACS 1996, 118, 3626
Hartwig Inorg. Chem. 2007, 46, 1936

4-Center Reactions Summary of Key Features

L nM(a)

X + A-B

L nM(a)

L nM(a)

A +

B-X

Requires open coordination site.

No change in oxidation state of the metal.
Cleavage of M-C bond proceeds with retention of configuration.

Me

Me

N
Cp2Zr

PhSiH 3

Me

Me

N
Cp2Zr

H 2(Ph)Si

H
H

Me

Me

Cp2ZrSi(Ph)H2

Me
Jordan OM 2005, 24, 2688

Cp*

Cp*

Ru

Ru
Ph 3P
Ph 3P

Ph 3P
Ph 3P

Me

Cp*
Me
Ru
Bcat

Ph 3P
Ph 3P

+ MeBcat
H

O
+

H-B
O

HBcat
Hartwig, JACS, 1994, 116, 1839
Review: Waterman OM 2013, 32, 7249

Migratory Insertion Reactions Basic Summary-CO

O
carbon
monoxide
insertions

C
LnM

LnM

!Although the reaction is usually referred to as a carbon monoxide insertion reaction, mechanistic studies have
shown that it actually takes place by an alkyl migration pathway.
!Requires cis orientation of R, CO.
!Relative migratory aptitude:

LnM

CH3 >

LnM

sp3 carbon

>>

LnM

CF3

LnM

very rare

sp2 carbon

This trend reflects relative metal-X bond strengths.

!Proceeds with retention of configuration at migrating carbon.

t-Bu
H D

Fe(CO)2
Cp

Ph3P
THF

t-Bu

CO
Fe

H D
O

Cp PPh3
Whitesides JACS 1974, 96, 2814

Migratory Insertion Reactions Basic Summary-Alkene/Alkyne

forward: insertion of olefins and
alkynes into M-H and M-R'
LnM

LnM
R

reverse: For R= H, -hydride

elimination reactions

!!Requires cis orientation of R, alkene.

!!Cis addition of LnM, R.
!Relative migratory aptitude: LnM-H >> LnM-CH3 (kinetic effect). In the best studied system to date, kHmig/kRmig
~107-108. Although the latter is the key step in Ziegler-Natta polymerization of olefins.
Brookhart JACS 1988, 110, 8719

!!Relative rate of insertion:

R
>>

R
>

R
>

>

R
>

>>
R

CHNF, Ch 6

Migratory Insertion Reactions--Summary--Hydride Elimination

R

-hydride
R elimination
LnM

LnM

R'

R'

!Requires open coordination site. Relatively slow for coordinatively saturated complexes. One manifestation of
this can be seen in changing from simple phosphines to chelating bis-phosphines. This inhibits phosphine
dissociation and keeps the complex coordinatively saturated.
!Principle mode of decomposition for metal alkyls.
!Important step in olefin isomerization.
!Shows geometric effects; slower in metallacyclic compounds.

L2Pt

L2Pt

L2Pt

nBu
nBu

L2Pt +

H3C

krel
1

L2Pt +

H3C

L2Pt

CH3

H3C

L2Pt + H3C

Optimum transition
state has Pt, H and
the 2 C's coplanar

best when
H-C-C-Pt
angle is 0
L2Pt

1
4

10-4

Cf. Crabtree

CHNF, Ch 6

Catalytic Cycles-1-Hydrogenation
Ln+1M

Ligand-loss
(exchange)

LnM

+ H2

Oxidative-Addition

18 e-

LnM

16 e-

+2

Ligand-loss
(exchange)

-L
H
+2

Ln-1M
16

+2

Insertion

e-

Ln-1M

CH3

H
H

Ligand-add
(exchange)

+2

16 e-

Ln-1M

18 e-

Ligand-add
(exchange)

+L
H
+2

LnM
18

- C2H6

e-

CH3

LnM

Reductive
Elimination

16 e-

James in Comp. Organometallic Chem., 1982, Vol 8, Ch 51, p 285, CHNF, Ch 10

Catalytic Cycles-2-Hydroformylation
HRh(CO)2L2 18 e-CO Ligand loss
(exchange)
CHO
R

HRh(CO)L2

16 eR

red-elim

Ligand add
(exchange)

H
H

R
O

ox-add

Rh
CO

L
H

L 18 e-

Rh

Regiochemistry
Determining

insertion

H3C

Rh(CO)L2

CO
18 e-

+H2

migratory
insertion

Rh(CO)L2

CHO

16 eR

O
migratory
insertion

Rh(CO)L2 16 e+CO

Me
Iso

+H2 ox-add

Rh(CO)2L2
18 e-

H
R

Rh(CO)L2 red-elim
18 e-

CH3

olefin
hydrogenation

Stille Comp. Org. Syn., Vol 4, Ch 4.5, p 913

Catalytic Cycles-3-Heck Aminocarbonylation of Aryl Halides

Ar-X

HN(R1)R2

solvent, Base (B:), CO

N(R1)R2

Ar

L/ Pd

L2Pd

Ar

N(R1)R2

BHCl

14

RE

RE
+ Ar-Cl

OA

B:

O
L2Pd

Ar

Cl

Ar

Cycle B

16

L2Pd
Cl

N(R1)R2

Cycle A

L2Pd
16

16
MI
BHCl

+ CO

LE

O
O

B:

Ar

L2Pd
X
Review: Barnard OM 2008, 27, 5402

HN(R1)R2

16

Ar

Nucleophilic Attack or
Reductive Elimination

N(R1)R2

Background Material for 5.44

The 18 Electron Rule

Consider a complex MLn:

A stable electronic configuration is achieved

if all bonding and non-bonding MO's are filled.

n+1 p

n+1 s

nd

9n
non-bonding

Ln

n ML
bonding

Mitchell, Parish J. Chem. Ed. 1969, 46, 811

Examples

ZrCp2

ZrCp2

Cp

Cp

Zr4+

Zr2+
Cp

Cp

ZrII d2

2 x Cp
2-benzyne

12
2
16 e

ZrIV d0

0
2 x Cp
12
benzene dianion
4
16 e

Backbonding does not change e count, but it does change formal oxidation state.
An example of why oxidation state is really only a formalism
in organometallic chemistry (although often a useful one)

Metal-Ligand Complex Geometries

Five coordinate:

Six coordinate:
cis
L
trans

L
L

Leq

Leq

Lax

L
Leq

L
L

Lax

Four coordinate:
trans
L
L
L

L
L

tetrahedral

L
cis

M
L
square
planar

L
L

square
pyramidal

trigonal
bipyramidal

octahedral

d8 Square Planar Complexes

ClRh(PPh3)3

PdCl2(PR3)2

(Wilkinson's catalyst)

Ph3P

Cl

Cl

Ir
OC

Pd
PPh3

Pd
Cl

All are stable, 16 ecomplexes.

Square planar geometries:
L

X
M

But Pd(PPh3)4 is tetrahedral (a d10 complex)

[Very] Simple MO Theory

z

Octahedral ML6:

dz2

dx2-y2
eg

is larger for:
1. 2nd and 3rd row TM's
2. "strong ligands"--e.g.,
CO (-effects), Ph3P, H(more electron density,
accentuates LF effects)

6 et2g

12 e-

See Crabtree, Ch 1, 2

Ligand-centered

dxz

dyz

dxy

MO Diagram for an Octahedral Complex

y
x

L
L

L
M

L
L

L
d6 octahedral

dx2-y2, dz2

dxy, dyz, dxz

MO Diagram for Tetrahedral

d8

Complex

L
L

M
L
z

y
x

dxy, dyz, dxz

dx2-y2, dz2

Effect of -Bonding on Orbital Energies

if -Backbonding
eg

if -Donation

eg

eg

eg

t2g

t2g

t2g
t2g
More tendency to be 18 e-

electron density is
removed from the metal,
lowering the energy of
these orbitals (by mixing
with the empty ligand *)
See Crabtree, pp17-19

interaction with
filled ligand
orbitals, raises
the energy of
these orbital
(electron-electron
repulsion)

MO Diagram for
Square Planar d8 Complex

L
z

y
x

dxy
(between x-y axis)

2 2
d x -y

(sits on x-y axis)

ligand centered