Chapter 2

Complexes with metal-carbon

Bonds
Metal alkyls, aryl, hydride and
related -bonded ligands
By Indah Raya

Outline
1. The stability of transition metal-carbon bonds
2. Preparation of complexes with metal-carbon bonds
3. Chemical properties of complexes with metal-carbon bonds
4. Related -bonded ligands complexes
[ M-X (X = SiR3, OR, NR2, F, Cl, etc.) ]
5. Metal hydrides

References and suggested readings:

1. The Organometallic Chemistry of the Transition Metals, Robert H. Crabtree,
3rd Edition, 2001, Chapter 3
2. Organometallic Chemistry, G. O. Spessard, G. L. G. L. Miessler, PrenticeHall: New Jersey, 1997, Chapter 6
3. Organotransition Metal Chemistry, Akio Yamamoto, 1986. Chapters 3.1, 4.2.

1. The stability of transition metal-carbon bonds

Formation and breaking of metal-carbon -bonds is the central
event in organometallic reactions and in many organic reactions
catalyzed by transition metal complexes.
Prior to 1960s:
Non-transition metal
alkyls are well known,
e.g.

Me
Me

Me
Al

Al
Me

Me
Me

AlMe3 ZnEt2 (1848)

Transition metal
alkyls are rare.
Only a few
transition metal
alkyls were
prepared. e.g.

Pope, Peachey, in 1909:

[Me3PtI]4

PtCl4 + 4 MeMgI
[Me3PtI]4:

I
Me3Pt

Me3
I
Pt
PtMe3
I

PtMe3

Attempts during the 1920s through 1940s to make

further examples of TM alkyls all failed.

These failures led to the view that transition metalcarbon bonds were unusually weak.

Are transition metal-carbon bonds weak and unstable?

But today: Transition metal-carbon bonds are known for
virtually all transition metals.

Questions
Are transition metal carbon s bonds really unstable?
What affects M-C bond strength?
What causes the earlier failure to obtain transition metal alkyls

stability
thermal
CH4 + O2 CO2 + H2O

kinetic
G < 0, thermally unstable
Kinetically stable

The thermal stability can be related to bond dissociation energy.

M-X (g) M(g) + X(g)

H = BDE (M-X)

If BDE (M-X) is large, M-X is thermally more stable.

Range of M-C bond dissociation energy (BDE).

BDE (M-C) values in MRn complexes (KJ/mol)
Non-transition metals
Transition metals
M-C bond BDE
Compound
M-C bond
Li-Et
209
Ti(CH2C(CH3)4
Ti-CH2R

BDE
170

Li-Bu

248

Ti(CH2Ph)4

Ti-CH2R

240

Zn-Me

176

Ti(CH2Si(CH3)4

Ti-CH2R

250

Zn-Et

145

Cp2Ti(CH3)2

Ti-CH3

250

Cd-Me

139

Cp2TiPh2

Ti-Ph

350

Hg-Me

122

(CO)5MnCH3

Mn-CH3

150

Hg-Et

101

(CO)5ReCH3

Re-CH3

220

Zr(CH2C(CH3)4

Zr-CH2R

220

Hg-i-Pr

89

Hg-Ph

136

Zr(CH2Ph)4

Zr-CH2R

380

B-Me

363

Zr(CH2Si(CH3)4

Zr-CH2R

225

B-Et

342

CpPt(CH3)3

Pt-CH3

165

Al-Me

276

(Et3P)2PtPh2

Pt-Ph

250

Al-Et

242

Ta(CH3)5

Ta-CH3

260

Ga-Et

237

W(CH3)6

W-CH3

160

Non-transition metals:
BDE(M-C): 89-280 kJ/mol
[Except B-C]
Transition metals:
BDE (M-alkyl) : 150 - 260
BDE (M-aryl): 250 - 350
Normally, BDE (M-alkyl) <
BDE (M-aryl)
Conclusion: Transition
metal-carbon bond energies
are not so different from
those of main group metals.

2). Factors affecting M-C bond strength

Affecting Factors :

LnM

M effect;
Ln effect;
R effect;

a) Metal effect

C-(sp3, sp2, sp) effect.

For main group metals, BDE (M-CH3), kJ/mol

B-Me

363

Zn-Me

176

Al-Me 276

Cd-Me

136

Ga-Me 247

Hg-Me

122

BDE(M-C) decreases when going down a group.

 For transition metals, BDE (M-CH3), kJ/mol,

(CO)5Mn-CH3

150

(PhCH2)3Ti-CH2Ph

240

(CO)5Re-CH3

220

(PhCH2)3Zr-CH2Ph

380

BDE(M-C) increases when going down a group.

b) R effect (M-R):

Relative bond strength:

Bond dissociation energies D[R-Mn(CO)5]

Complex
BDE[RMnCO)5]
(kJ/mol)
[Mn(CO)5CF3]
172

(M-Cl > M-Br > M-H = or > M-I)

[Mn(CO)5C6H5]

170

M-COCH3

[Mn(CO)5CH2C6H5]

87

[Mn(CO)5CH3]

153

[Mn(CO)5COCH3]

129

[Mn(CO)5COC6H5]

89

more electron-withdrawing R.
* M-H is stronger than M-CR3

[Mn(CO)5COCF3]

147

[Mn(CO)5H]

213

s orbital is indirectional and more dense.

[Mn(CO)5I]

195

[Mn(CO)5Br]

252

[Mn(CO)5Cl]

294

M-H > M-CF3 > M-Ar > M-CH3 >

M-C-R: stability increases with

* M-CF3 is stronger than M-CR3

note,F is electron withdrawing.
* M-Ar is stronger than M-CR3.
back-donation for M-Ar.

Would you expect M-CH3 bond be stronger or weaker than

M

Why
alkynyl
(acetylide complexes)

alkenyl
(vinyl complexes)

*
Evidence:
PMe2Ph
Cl

Pt

208 pm

CH2SiMe3

PMe2Ph

Cl

PMe2Ph

PMe2Ph

203
Pt
CH 135 pm
127o
CH2
PMe2Ph

118 pm
198
Pt
C
CH

Cl

PMe2Ph

Would you expect M-CH3 bond be stronger or weaker than

M

Why

alkenyl
(vinyl complexes)

alkynyl
(acetylide complexes)

(answer: M-CH3 < M-CH=CH2 < M-CCH)

* M-CH3:

no d-p interaction;

M-CH=CH2: one d-p interactions;

M-CCH:

two d-p interactions

* Evidence:
PMe2Ph
Cl

Pt

208 pm

CH2SiMe3

PMe2Ph

Cl

PMe2Ph

PMe2Ph

203
Pt
CH 135 pm
127o
CH2
PMe2Ph

118 pm
198
Pt
C
CH

Cl

PMe2Ph

Stability of the following M-C bonds:

M-CH3 < M-CH2-NO2
Why ?

Stability of the following M-C bonds:

M-CH3 < M-CH2-NO2
Why ?

Electron-withdrawing group
Encourage backdonation

M
M

Summary:
The M-C bond in transition metal alkyl complexes is not as weak as
was thought previously.
There is no inherent instability of transition metal alkyls.
The BDE(M-R) value increases as the atomic number increases among
the congeners in the same group, in an opposite trend to non-transition
metal alkyls.
The D(M-R) value decrease in the order M(M-H) > D(M-CF3) > D(M-Ph) >
D(M-CH3) > D(M-CH2CH3) > D(M-CH2Ph).
The earlier failure in obtaining TM alkyls is not due to thermodynamic
reasons !

Exercises
Which one has the strongest stability of the following complexes ?

a)

OC

Fe
CH3

OC

Ru
CH3

CO

b)

OC

OC

Fe

OC

CH3

CH3
CO

Fe

OC

CH2CH3

OC

Fe
CH3
CO

Fe
CH2NO2
CO

CO

Fe
CO

OC

CO

CO

c)

Os

OC

Fe
CO

Exercises
Which one has the strongest stability of the following complexes ?

a)

OC

Fe
CH3

OC

Ru
CH3

CO

b)

OC

OC

OC

CH3
CO

CO

Fe

OC

CH3

Fe

OC

CH2CH3

Fe
H

OC

Fe

CO

[Answer: a) last one

CH3

Fe
CH2NO2
CO

CO

CO

c)

Os

OC

CO

b) last one

Fe
CO

c) first one]

3). Origin of earlier failure in obtaining TM alkyls:

(Kinetic consideration)
General questions.
Q1. Why could many TM alkyl complexes not be isolated?

Q2. What are the

common
decomposing
pathways for

C
C

transition metal
alkyls?

L nM

R
X

MLn
X = R, H , ....

+ R

3). Origin of earlier failure in obtaining TM alkyls:

(Kinetic consideration)
General questions.
Q1. Why could many TM alkyl complexes not be isolated?
There are many pathways that TM alkyl complexes can be decomposed.

Q2. What are the

*. -elimination (The most common route!)

common
decomposing
pathways for
transition metal
alkyls?

C
C

*. Reductive elimination
L nM

R
X

MLn

+ R

X = R, H , ....

*. Others,
e.g. -eliminations, intramolecular reactions.

Q3. How can we obtain stable M-alkyl complexes?

Stable M-alkyl complexes could be obtained if the above decomposing
pathways can be prevented.
-elimination.
The most common decomposition pathway for alkyls is -H elimination,
which converts a metal-alkyl into a hydrido-olefin complex.

C
C

hydrido-olefin complex

What is the condition for -H elimination to occur ?

A. There must be a -H.
B. The complex should be able to form four-membered co-planar
transition state (see (A))
M

C
H

(A)

(B)

(C)

C. There is a vacant site cis to the alkyl (e.g. (B). but not (C)).
(need an empty orbital to accept C-H electron.)
D. The olefin formed is stable.
E. The metal has e- to go to *(C-H).

Exercises.
(a). It is difficult for the following compounds to undergo hydrogen eliminations. Suggest main reasons.
PEt3
(1)

Cl

Pt

C C H

PEt3
16e

(2)

(3)

OC
OC

R
N

Fe

H2C

N
R2

Co

C
H2

CH3

CH3
R
N

N
OH2 R2

-H2O

R
N

H2C

N
R2

Co

CH3
R
N
N
R2

PEt3
(1)

Cl

Pt

Et3P
16e-

C C H

* Can not form four-membered

transition state
*After b-H elimination,
unstable C C is formed

(2)
OC
OC

Fe

- CO

Fe

CO
CO

C
H2

* No vacant site cis to the alkyl

CH3

CH2CH3

CO

Fe
CH2CH3

18e
16e
CO

CO

Fe
H

CO

CO

Fe
H

CO

Fe
CH2

H
H2C

(3)

R
N

H2C

N
R2

Co

CH3
R
N

N
OH2 R2

-H2O

R
N

H2 C

N
R2

Co

CH3
R
N
N
R2

The vacant site is not cis to the alkyl group.

(b) Would you expect the following complexes to undergo b-H

elimination easily?

PEt3

PEt3
(1)

Cl

Pt

CH2

PEt3

(2)

Cl

CH3

PEt3

PEt3

PEt3
(3)Cl

Pt
PEt3

Pt

(4)Cl

Pt
PEt3

(b) Would you expect the following complexes to undergo bH elimination easily?
PEt3

PEt3
(1)

Cl

Pt

CH2

PEt3

(2)

Cl

CH3

Pt
PEt3

after -H elimination
is formed

PEt3

PEt3
(3) Cl

(4)Cl

Pt

Pt

PEt3
PEt3
after -H elimination after -H elimination
is
formed

Answer: (1) and (3)

or

is
formed

(c) Which of the following complexes would you expect to be least stable?

OC

Fe
CO
(a)

If an alkyl
compound can
undergo -H
elimination, it is
unstable.
For above
complexes to
undergo -H
elimination, the
right steps are
needed.

CH2CH3

Ph2P

Fe
PPh2
(b)

CH2CH3

Ph3P

Fe
PPh3
(c)

CH2CH3

(c) Which of the following complexes would you expect to be least stable?

OC

Fe
CO

Ph2P

CH2CH3

(a)

If an alkyl
compound can
undergo -H
elimination, it is
unstable.
For above
complexes to
undergo -H
elimination, the
right steps are
needed.

Fe
PPh2

CH2CH3

Ph3P

(b)

PPh3

CH2CH3

(c)

-L

Fe
L

Fe

CH2CH3

-L

Fe
CH2CH3

18e
16e
L

Fe
H

Fe
H

(a), hard to lose CO

(b), hard to lose PPh2 (chelating effect)
(c), can lose PPh3 easily.

Fe
CH2

H
H2 C

Conditions for -H elimination

A. There must be a -H.
B. The complex should be able to form four-membered co-planar
transition state (see (A))
M

C
H

(A)

(B)

(C)

Normally 16e species

C. There is a vacant site cis to the alkyl (e.g. (B). but not (C)).
(need an empty orbital to accept C-H electron.)
D. The olefin formed is stable.
E. The metal has e- to go to *(C-H).

For 16 electron complexes, prior ligand dissociation is not required with the
exception of Pd(II) and particularly Pt(II), which do not like to become 18e
complexes.
Thus rate of decomposition of (Ph3P)2PtBu2 to give butane and butene is inversely
dependent upon [PPh3].
The
platinacyclopenta
ne analog
undergoes
decomposition
10,000 times
more slowly.
However larger
platinacycles
undergo
decomposition at
a similar rate to
the dibutyl
complex and by
the same
mechanism.

Further notes on -elimination.

(i) -H elimination on d0 (electron deficient) metal complexes may
not occur. e.g.
Cl H2
C
CH2
Ti
P
Cl H
Cl
Me2

stable, why?

Me2
P

Ti

H2
C

agostic C-H interaction

H2C

CH2

Ti

CH2
H

Bonding in M(2-C-H)
M

CR3

CR3
H

(C-H)

M
H

(1)

CR3

(2)

*(C-H)

A C-H bond is broken!

Further notes on -elimination.

(i) -H elimination on d0 (electron deficient) metal complexes may
not occur. e.g.
Cl H2
C
CH2
Ti
P
Cl H
Cl
Me2

stable, why?

Me2
P

Ti

H2
C

agostic C-H interaction

H2C

CH2

Ti

CH2
H

Bonding in M(2-C-H)
M

CR3

CR3
H

(C-H)

M
H

(1)

CR3

(2)

A C-H bond is broken!

*(C-H)

The complex has no d

electron for
backdonation, so it is
difficult to undergo -H
elimination.

(ii) Other -elimination is also possible, e.g.

CH2

M
H

HC

M
-H elim.

CH3

CH2

H
C H

CH2

M
CH2
-CH3 elim.
CH3
CH3

favorable

M
H H

CH2
C

because:

-H elim.

CH2 CH2

-F elim.

F
favorable

M
F

CH2
CH2

(ii) Other -elimination is also possible, e.g.

CH2

M
H

HC

M
-H elim.

CH3

CH2

H
C H

CH2

M
CH2
-CH3 elim.
CH3
CH3

favorable

M
H H

CH2
C

-H elim.

CH2 CH2

-F elim.

M
F

CH2
CH2

favorable

because: M-H > M-CH3 (by 15-25 kcal/mol); M-F > M-H

Summary. Metal-alkyls that are stable to -hydrogen

elimination

1. Alkyls that do not have -hydrogens

2. Alkyls for which the -hydrogen cannot approach the metal

center (as in cyclic alkyls or as a result of steric crowding)

3. Alkyls in which the M-C-C-H unit cannot become coplanar

4. Olefin generated is unstable

5. 18-electron species that cannot dissociate a ligand

6. Some d0- alkyls

b) Reductive elimination
LnM

R
X

+ R

MLn

X = R, H , ....

Coordination number decreases by 2.

* Oxidation number decreases by 2.
The process is the second most common decomposition pathway
for metal alkyls. e.g.
PR3
I
Me
Me
R3P

Pt

Me

Me

PR3
Au

Me
Me

R3P

Pt

R3P Au

PR3
Me

+ H3C CH3

Me + H3C CH3

More detailed discussion will be given later.

c) Other pathways
M

-H elimination
For early transition
metal alkyls, hydrogen
elimination can be
an important
decomposition
pathway.

Example

Cp

H
R

H
R

Mo

Cp
Cp
Cp

PR3

CH3

+
Cp

Mo

Cp

H
C PR3
H2

Cp

Mo

H
CH2

C
+

PR3
+

Mo

C
M

Cp

CH3
- PR3

Another example,
H
Cl
Cl

CH2Ph
Ta CH Ph
2
CH2Ph

LiCp*
Ta

- Ph-CH3

Cl

Cl

Ph

CH2Ph

- Ph-CH3

LiCp*

CH2Ph
Ta CH Ph
2
CH2Ph

Cl

H Ph
C
H or
Ta
CH2Ph
Cl
CH2Ph
(a)

Which intermediate is more likely?

C Ph
Ta H
CH2Ph
CH2Ph
(b)

Another example,
H
Cl
Cl

CH2Ph
Ta CH Ph
2
CH2Ph

LiCp*
Ta

- Ph-CH3

Cl

Cl

Ph

CH2Ph

- Ph-CH3

LiCp*

CH2Ph
Ta CH Ph
2
CH2Ph

Cl

H Ph
C
H or
Ta
CH2Ph
Cl
CH2Ph
(a)

Which intermediate is more likely?

(a). The OS of Ta in (b) is too high?

C Ph
Ta H
CH2Ph
CH2Ph
(b)

-H elimination. e.g.
CH3
R3P
CH2 CH3
CH
R3P
3
CH2 C
Pt
C
Pt
CH3
R
P
3
CH2 CH
R3P
CH3
CH2
3
C CH3
CH3 C CH3
H3C CH
3
CH3
CH3
CH3 C CH3
CH3
CH3
H
CH2 C CH3
R3P
CH3
Pt
CH2
R3 P
CH2 C CH3
CH3

Summary: Common pathways of decomposing M-alkyls:

-H elimination
Reductive elimination
Others.

Exercises.
1) For each pair of complexes listed below, which one is less stable?
H3 C
(1)

(2)

H3C

H 3C

CH3
CH3

CH3
(a)

OC
OC

CH3
PPh3

(a)

(3)
OC
Ph3P

(a)

CH2-CH3
PPh3

OC
OC

CH3
CO

(b)

OC
OC

CH2-CH3
PPh3

(b)

OC
Ph2P

(b)

CH2-CH2-CH3
PPh2

Exercises.
1) For each pair of complexes listed below, which one is less stable?
H3 C
(1)

(2)

H3C

H 3C

CH3
CH3

CH3
(a)

OC
OC

CH3
PPh3

(a)

(3)
OC
Ph3P

(a)

CH2-CH3
PPh3

OC
OC

CH3
CO

(b)

OC
OC

CH2-CH3
PPh3

(b)

OC
Ph2P

(b)

CH2-CH2-CH3
PPh2

Answer:
(1) (a)
reductive
elimination.
(2) (b) -H
elimination.
(3) (a) -H
elimination
is easier

2) Which one is least stable ?

Ru
R 3P

CH3 R P
3

PR3
(a)

Ru

Ru

CH2CH3 R P
2

CH2CH3

PR3

PR2

(b)

(c)

3) which one is most stable ?

Ru
R3P

CO
(a)

CH3

Ru
R3P

CO
(b)

CH2CH3

H3C

Ru

R3P
(c)

CH3
CH3

PR3

2) Which one is least stable ?

answer: (b)
Ru
R 3P

CH3 R P
3

Ru

PR3
(a)

CH2CH3 R P
2

Ru

CH2CH3

PR3

PR2

(b)

(c)

3) which one is most stable ?

Ru
R3P

CO
(a)

CH3

Ru
R3P

CO
(b)

CH2CH3

-H elimination

answer: (a).
H3C Ru CH3
CH3
R3P PR3
(c)

(b) will undergo

-H elimination
and (c) will
undergo R. E.

2. Preparation of complexes with metal-carbon bonds.

A. Synthesis by alkyl transfer reactions.
R- + M-X ---------> M-R + XB. Synthesis from anionic transition metal
complexes.
M- + R-X ---------> M-R + XC. Synthesis by oxidative addition reactions.
M + R-X -----------> X-M-R
D. Synthesis involving insertion Reactions.
M-X + A -----> M-A-X
E. Synthesis involving elimination reactions.
M-A-R ------> M-R + A
F. Synthesis by attack on coordinated ligands

A. Synthesis by alkyl transfer reactions

R- + M-X ---------> M-R + XTypical R- reagents: RLi, RMgX, AlR3, AlR2X, ZnR2, etc.
Examples:
Preparation of
homoletic alkyl
complexes:

Cl
Cl
Cl

Cl

Cl

Me
+ LiMe

Me
Me

Cl

Me

CH2Ph

Ti

Cl

+ PhCH2MgBr

Cl

PhCH2

Ti

CH2Ph
CH2Ph

Ph

Cl
Cl

+ LiCl

Me

Cl
Cl

Me

Zr

Cl
Cl

+?

Ph

Zr

Ph
Ph

A. Synthesis by alkyl transfer reactions

R- + M-X ---------> M-R + XTypical R- reagents: RLi, RMgX, AlR3, AlR2X, ZnR2, etc.
Cl

Examples:

Cl

Preparation of
homoletic alkyl
complexes:

Cl

Cl
Cl

Me
Me

+ LiMe

Cl

Me

CH2Ph

Ti

Cl

+ PhCH2MgBr

Cl

PhCH2

Ti

CH2Ph
CH2Ph

Ph

Cl
Cl

Me

+ LiCl

Me

Cl
Cl

Me

Zr

Cl

+?

Ph

Zr

Ph
Ph

Cl

PhLi or PhMgBr

Note: different alkylating agents may have different reactivity, e.g.

Cl
Cl

Ti

Me
Cl
Cl

+ MeLi
Me

Cl

Me
Me

Cl
Ti

Ti

Cl
Cl
Cl

+ AlMe3
Me

Ti

+ AlMe2Cl

Cl
Cl

CrCl3(THF)3 + MeMgBr

CrMe3(THF)3

CrCl3(THF)3 + AlMe3

CrMeCl2(THF)3

ZnR2isalsoaweakalkylatingreagents.e.g.
Cl

Cl

Nb

Cl
Cl

Cl

+ ZnMe2

Cl

Cl

Nb

Me
Me

Cl

Example. Preparation of alkyl complexes:

R- + LnMXy ---------> LnMRy + XPh
P
P
Ph
Ph3P
Ph3P

Ph

Ph
Ni

Cl

+ MeLi

Cl

Ph

Pt

Cl

Ph
?

Ph3P

Cl

M Cl
Cl
M = Ti, Zr, Hf

Ph

Ph3P

Ni

Ph

Pt

?
M R
R
R = Ph, CCPh

Me
Me

Example. Preparation of alkyl complexes:

R- + LnMXy ---------> LnMRy + XPh
P
P
Ph

Ph3P
Ph3P

Ph

Ph
Ni

Cl

+ MeLi

Cl

Ph

Pt

Cl

Ph

Ph3P

Cl

M Cl
Cl
M = Ti, Zr, Hf

Ph

Ph3P

Ni

Ph

Pt

?
M R
R
R = Ph, CCPh

Me
Me

Li(CH2)4Li

PhLi, or PhMgBr
PhCCLi, or
PhCCH/base

B. Synthesis from anionic transition metal complexes.

M- + R-X ---------> M-R +
X-

CH3

Examples:

+ Me-I

CO
OC

Mn

OC

CO

Mn

OC

CO

+ I-

CO

CO
O

CO
CO

O
CF3

OC
Cl

C
Mn

OC

CF3
CO
CO

CO

+ Cl-

Generation of LnMCO
OC
OC

Mn

CO
OC

CO
Mn CO

OC Mn

Na

CO

O
C

OC
Fe

C
O

Na
Fe

OC

CO
CO

CO

Fe -

OC

CO

CO
Mo

CO
CO

CO

CO

OC

CO

CO

OC

Na+
OC

MoOC

CO

Exercise. Suggest reagents for the following preparations.

CO
OC

OC

CO

CO

OC

OC

CO

O
C

OC
Ru

C
O

Et
CO

Ru
CO

OC

Ru
OC

Me

Exercise. Suggest reagents for the following preparations.

CO
OC

OC

CO
CO

OC

CO
-

OC

CO

Et
CO

Na+

EtI

MoOC

OC

OC

W
OC

Et
CO

O
C

OC
Ru

C
O

Ru
OC

CO

Ru

Me

OC

Na
MeI
OC

RuOC

OC

Ru
OC

Me

C. Synthesis by oxidative addition reactions.

Typical oxidative addition reactions:
+

LnM

LnM

O.S. = 0

O.S. = 2

16e

18e
C.N. = n+2

C.N. = n

Examples of preparation of complexes.

R 3P
Br

CO
Ir

R3P

+ CH3Br

Br

PR3

R3 P

PR3

18e
H 3C

Pt

CO

Ir
Br

16e
R 3P

CH3

+ CH3I

PR3

H 3C

Pt
I
PR3

PR3
Pt

R3P

For d8, bulky phosphine

Examples of preparation of complexes.

Ph3P
Ph3P

Pt

PPh3

MeI

Examples of preparation of complexes.

Ph3P
Ph3P

Pt

PPh3

MeI

Ph3P
Ph3P

Me
Pt

- PPh3
I

Ph3P
Ph3P

PPh3

I
Pt
Me

or

Ph3P
I

Me
Pt
PPh3

Cyclometalation, a closely related reaction. Synthesis by

oxidative addition of C-H bonds.

16e

16e

18e

d8, 16e

18e

d8, 16e

D. Synthesis involving insertion Reactions.

M-X + A -----> M-AX

Examples:

H
OC

Mn

OC

CO
CO

CH2
+ CH2N2

Cp2Zr

Mn

OC

CO
Cl

OC

CO
CO

CO
+ CH2=CH-R

Cp2Zr

Cl
CH2 CH R
H

Cp2Mo

H
H

NC
H

H
CN

H
Cp2Mo
CH
CN

CH2 CN

PEt3
Cl

Pt

+ F2C CF2

+ F2C CH2

PEt3
PEt3
Cl

Pt
PEt3

PEt3
Cl

Cl

Pt

PEt3
H

+ F2C CF2

Cl

Pt

PEt3

PEt3

PEt3

PEt3

Pt

+ F2C CH2

Cl

PEt3

Pt

F2
C CF2H

F2
C CH3

PEt3
PEt3

not Cl

Pt
PEt3

H2
C CF2H

E. Synthesis involving elimination reactions.

M-A-R ------> M-R + A

(A should be very stable)

A = CO, CO2, SO2, N2, e.g.

CO
OC
OC

Cl

CO

CO

O
C
CH3

Mn
CO

PPh3
CO O
Ir
S

Cl

OC

Mn

OC

CO
CH3 + CO

CO
PPh3
CO
Ir

Cl
Cl

O
PPh3

PPh3

PEt3
Cl

Pt

PEt3
Cl

N N

Et3P

OC

+ SO2

Pt

+ N2

Et3P

Ru
OC

C
O

CH3

OC

Ru
OC

+ CO
CH3

F. Synthesis by attack on coordinated ligands

+
Fe

OC
Ph3P

CH3

Equivalent to Ph-

Li2[Cu(CN)Ph]
Fe

OC
Ph3P

H3C

OC

CO

Ph
CH3
Note the geometry

+
Fe

CH3

+ :NuOC

We will go to more details later.

Fe
CO

Nu

3. Chemical properties of complexes with metal-carbon bonds

(1) -hydrogen elimination

LnM

LnM

L
LnM

Ru

OC
Ph3P

+ LiCH2CH2CH2CH3
Cl

OC

How?

Ru
H

PPh3

Ru

OC
Ph3P

+ LiCH2CH2CH2CH3

Ru
OC
CH2CH2CH2CH3
- LiCl Ph3P
18e

Cl

18e

- PPh3

OC

Ru

CH2CH2CH2CH3

16e

Note: 18 16 18 .
OC

Ru

18e

CH2CH3
+ PPh3

OC

Ru
H

PPh3

+ H2C CHCH2CH3

For d8 complexes, possibly

16 14 16.

(2) Reductive elimination

+ RX
X = R, H, ........

e.g.

Me
L
Ph

Rh
I

CO

CO + Me
Rh
L

Ph

(3) , -elimination, e.g.

Ph

Cl
PhCH2

Ta
Cl

CH2Ph
CH2Ph

+ TlCp

Ta

how?

Ph

(3) , -elimination, e.g.

Ph

Cl
PhCH2

CH2Ph

Ta

Ta

+ TlCp

CH2Ph

Cl

Ph

Cl
PhCH2 Ta
Cl

how?

CH2Ph
CH2Ph

PhH2C

+ TlCp

M-Cl + Tl+
TlCl

Ta

CH2Ph

+ TlCl

CH2Ph

Ph
CH
PhH2C

Ta

H2C
Ph
(TS)

Ph
+ CH3Ph

Ta
Ph

CHPh
not PhH2C

Ta

H
CH2Ph

why ?

(3) , -elimination, e.g.

Ph

Cl
PhCH2

Ta
Cl

CH2Ph

Ta

+ TlCp

Ph

Cl
PhCH2 Ta
Cl

how?

CH2Ph

CH2Ph
CH2Ph

PhH2C

+ TlCp

Ta

CH2Ph

+ TlCl

CH2Ph

Ph
CH
PhH2C

Ta

H2C
Ph

CHPh
not PhH2C

Ta

why ?

CH2Ph

(TS)

O. S. of Ta is too high

Ph
+ CH3Ph

Ta
Ph

(4) Migratory insertion

CH3
OC
OC

Mn
CO

CO
CO

+ CO

OC
OC

C
Mn

CH3
CO
CO

CO

The insertion of CO into an M-C bond results in formation of an acyl

ligand. This is one of the industrially important reactions of metal alkyls.
Mechanistically, it involves intramolecular nucleophilic attack by the alkyl
on the carbon of CO. More discussion later.

Carbon dioxide can give mono- and bidentate

insertion products:

Insertion of alkenes.
Polymerization of olefins, one of the most important catalytic
industrial processes, relies on the facile insertion of alkenes
into metal-alkyl bonds:

(5) Electrophilic attack on alkyls

-

LnM R + E

+
LnM

+ E-R

(E+ = H+, Br+ (from Br2), HgCl+ (from HgCl2), even CHCl3 ....)

Two possible pathways:

LnM R E

+
or LnM R
E

+
LnM

-As the metals electronegativity increases, the nucleophilic reactivity of the MC bond decreases.
-Nucleophilic reactivity decreases with more stable carbanions (i.e. -CH 3 <
-C6H5 < -CCR).
Early transition metal alkyls are very sensitive to water and oxygen.
Late transition metal alkyls are more stable to water and oxygen.

Cl-

O
Examples.

Ru

OC
OC
O

+ HCl

+
Ru

Me

Ru
OC
Cl
OC

OC
OC

HBF4
BF4+
Ru

OC
OC

BF4-

O
+
Ru

OC
OC

..

:F:

..
:F

..

B
:F:
..

..
F:
..

BF4- is a weakly coordinate anion.

Other weakly coordinate anions: BPh4-, PF6-, AsF6-, SbF6-,

Exercises. Predict the products of the following reactions:

CH2CH3

Zr

Cl2

Cl

CH2CH3

Zr

HCl

Cl

CH2CH3

Zr

H2O2

Cl
O
Zr

C CH3
Cl

HCl

Exercises. Predict the products of the following reactions:

CH2CH3

Zr

Cl2

Cl
Zr

Cl

Cl

CH2CH3

Zr

HCl

Zr

+ ClCH2CH3

Zr

+ CH3CH3

Cl

H2O2

OH
Zr
Cl

Cl

+ HOCH2CH3

O
Zr

C CH3
Cl

HCl

Cl-Cl

Cl

Cl

CH2CH3

Cl
+

Zr
Cl

C CH3

HO-OH,
like Cl-Cl

(6) Special properties of some M-R complexes

Small metallocylcles show interesting
rearrangement.
CH2
LnM

CH2
CH2

LnM

CH2
CH2

CH2
Precusors to carbene

CH2

CH2

CH2

L nM

CH2

LnM
CH2

CH2
LnM
CH

CH2

CH2
CH2

CH2
CH

CH2
LnM

CH2

CH2

CH2

LnM

CH2
CH2

CH
HC

Larger metallacylcles show

normal properties of alkyls,
e.g.

CH2

4. Related -bonded ligand complexes

M-SiR3, M-OR, M-NR2, M-F, M-Cl, M-BR2

A. M-SiR3
*M-Si bond are longer than M-C
* BDE(M-SiR3) may be stronger than BDE(M-CR3)
Reason:
a) some -interaction (Si has empty d orbitals)
b) M-SiR3 is less sterically congested.
*Can LnM-SiCH2R undergo -H elimination?
LnM Si

LnM Si
H

LnM
H

Si
C

LnM

Si
C

In general, M-SiR3 has properties similar to M-CR3.

Si

filled

unfilled

4. Related -bonded ligand complexes

M-SiR3, M-OR, M-NR2, M-F, M-Cl, M-BR2

A. M-SiR3
*M-Si bond are longer than M-C
* BDE(M-SiR3) may be stronger than BDE(M-CR3)
Reason:
a) some -interaction (Si has empty d orbitals)
b) M-SiR3 is less sterically congested.
*Can LnM-SiCH2R undergo -H elimination? Yes.
LnM Si

LnM Si
H

LnM
H

Si
C

LnM

Si

filled

unfilled

Si
C

Yes. But more difficult than M-R since Si=C bond is weaker than C=C
In general, M-SiR3 has properties similar to M-CR3.

B. M-OR, M-NR2, M-F, M-Cl, etc.

(1) Difference between M-CR3 and M-X
M-CR3

M-X

no d-p interaction

possible d-p

interaction
M-X bond is stabilized for 16e or less species (early TM)

unfilled

filled

OR

M-X bond is destabilized for 18e species

M
filled

X
filled

OR

Consequences:
M-X can stabilize complexes with less than 18e. e.g.
PR3
H
H

Ir H
PR3

16e, unstable

PR3
H
H

Ir Cl

PR3
16e, stable

t-Bu
OO t-Bu

t-Bu
t-Bu O O
Mo
O

O
O

Mo
O

Why?

14e, stable

bonding can make these complexes to formally have 18e.

Consequences:
M-X can stabilize complexes with less than 18e. e.g.
PR3
H
H

Ir H
PR3

PR3
H

Ir H
PR3

16e, unstable

Mo

PR3
16e, stable

16e, unstable

Ir Cl

PR3
H
H

Ir

PR3
"18e"

..
Cl

t-Bu
OO t-Bu

t-Bu
t-Bu O O

PR3

O
O

Mo
O

Why?

14e, stable

t-Bu
t-Bu O O
Mo
O

.. t-Bu
OO t-Bu
..
Mo

O O
O

"18e"

bonding can make these complexes to formally have 18e.

Note: bonding is normally not included in valence electron counting.

With high valent transition metals, -donation becomes important. M-O-C

angles approaching 120 or even 180 are common.

An angle near 120 suggests that the O is sp2 hybridized and OR- acting as a
4 electron donor .
An angle near 180 suggests that the O is sp hybridized and OR- acting as a
6 electron donor.

Linear alkoxide have sometime be considered to be

isoelectronic with the Cp ligand.

6e-

..
O:
..

6e-, if bonding

(2)SimilaritybetweenMCR3andMOR:
BothcanundergoHelimination.
CH2
CH2

CH2
CH2
H

R
CH

M
H

H
C R

+
M

CH2

H2C

O C
+ R
H
M

Use of the reaction.

LnM-Cl

+ R-CH2-O-

LnM-O-CH2R
Cl

H + O C

H
R

(ROH + base = RO-)

C. M-BR2 complexes

filled

R
B
R
unfilled

5. Metal hydrides, M-H

History
1931: H2Fe(CO)4 prepared by Hieber, although the structure was not accepted
initially.
1955-1964: Cp2ReH, (PR3)2PtHCl, and K2[ReH9] prepared showing that M-H bonds
do exist.
1984: Dihydrogen complexes discovered (M-H2).
A. Structural types of metal hydrides.
(1) Terminal hydride or classical hydride, e.g.
H

Mo

Zr

Cl

PR3
R3P
R3P

Ru

H
R3P

(2) Non-classical hydride or molecular hydrogen complexes (1984)

H
M
H

CO

PR3
R3P
H
H

Fe
R3P

OC

OC

Cr
OC

CO
H
H

Q1. Would you expect the H2 molecule in the following complex can
rotate freely? why?

PCy3
CO H
W
H
PCy3

OC
OC

Consider the bonding between M and H2.

M

H
H

1. e- from (H2) ---> (M)

H
H

2. e- from d(M) ---> (H2)

Q1. Would you expect the H2 molecule in the following complex can
rotate freely? why?

PCy3
CO H
W
H
PCy3

OC
OC

Consider the bonding between M and H2.

M

H
H

1. e- from (H2) ---> (M)

H
H

2. e- from d(M) ---> (H2)

No. Rotation will break the bond between M and H2

Q2. LnMH2 can have two forms, depending on M and L.

Rationalize the structural difference in the following pairs.
(a)

+
Ph2P

Ph2P
(b)

P
Ph2

In terms of bonding:

Fe

vs

PPh2 H

+
Ph2P

CO
Mo
H

PPh2 H
CO

Et2P

PPh2

Mo

vs

PPh2

P
Et2

PEt2
PEt2

H
H

Os

M
H

1. e- from (H2) ---> (M)

H
H

2. e- from d(M) ---> * (H2)

Q2. LnMH2 can have two forms, depending on M and L.

Rationalize the structural difference in the following pairs.
(a)

+
Ph2P

Ph2P
(b)

P
Ph2

In terms of bonding:

Fe

vs

PPh2 H

+
Ph2P

CO
Mo
H

PPh2 H
CO

Et2P

PPh2

Mo

vs

PPh2

P
Et2

PEt2
PEt2

H
H

Os

M
H

1. e- from (H2) ---> (M)

H
H

2. e- from d(M) ---> * (H2)

H-H bond will break when there is excessive backdonation from M to *(H2). For
(a), Os has stronger backdonating ability than (b).
For (b), Et is more electron-releasing than Ph, leading to stronger backdonation.

(3) "Hydrogen-bonding" type interaction:

-------- H-X complexes
M

e.g.

H
Si

H
N

Often the interaction can be represented as:

M

or

H
X

In terms of bonding:
similar to M( 2-H2)

For example,

Cl
Ph3P

H
Ru

Cl
PPh2
Cl

Ph3P

agostic

Mn

OC
OC R3Si

Me2P
Me2P

Ti

CH2
Cl H

Cl

agostic

CH2

Additional examples

N
Rh

Pt
L

OC
OC

Mn

SiHPh2
H

(4) Bridging hydrides

2-H

H
M

M
(bent)

3-H

H
M

Examples:

Cp2Nb

R3P
R3P

Re

NbCp2
H
H
H
H

Cp2
Lu
H

PR3

Re
H

PR3

Cp2Lu

LuCp2
H

M ?

For electron counting purpose, we can use the resonance structures like:
H

H
M

Exercise. 18e or not?

OC CO
OC
CO
Re
H
OC
OC Re
OC
OC

OC CO
OC
CO
Re

Re
H

H
CO
CO
CO CO

OC
OC
Re
OC
OC

Re
H

CO
CO
CO CO

For electron counting purpose, we can use the resonance structures like:
H

H
M

Exercise. 18e or not?

OC CO
OC
CO
Re
H
OC
OC
Re
OC
OC

OC CO
OC
CO
Re

Re
H

H
CO
CO
CO CO

OC
OC
Re
OC
OC

Re
H

CO
CO
CO CO

7(Re) + 4x2 (CO) + 1 (H) + 2 (Re-H) =18

(5) BH4-, BH3L, and AlH4- complexes. A variety structures are possible.
e.g. for BH4-

H
M

H
M H B
H

H
B
H

2BH4

1-BH4

H
B

3-BH4

H
H
M

H
M

B
H
4

M
H

H
B

M
2

H
M

B
H
M

H H
M

For electron counting purpose:

Ionic model:

H
+
M

- H
B
H
H

M(BH4) M+ + BH4H

+
M

B
H

M(BH4) MH + BH3

Covalent model:

+
M

- H
B

H
B

H
M

H
H

For electron counting purpose:

Ionic model:
H
+
M

M(BH4) M+ + BH4-

- H
B
H
H

+
M

2e

4e

- H
B

+
M

H
H

H
B
H
1e

6e

Covalent model:

M(BH4) MH + BH3
H
H
H
M
M
B H
B
H
H
H
H
3e

5e

B. Synthesis of metal hydride complexes.

(1) By protonation (require a basic metal complex)
2-

CO
Fe

HBF4
CO
CO

OC

H
OC Fe
CO

BF4-

CO

OC

CO

OC

H
W H
H

HBF4

W
H

Ph3P

PPh3

Ni

HCl

PPh3

CO
OC

+
H

Ph3P
Ph3P

BF4-

+
Ni

H
PPh3
+

Ph2P
Ph2P

Ru

HBF4
H

Fe

Ph2P
Ph2P

Ru

H
H

BF4-

Cl-

(2) From hydride donors

M-X + H- donor ----------> M-H + XTypical H- donors: NaH, LiAlH4, NaBH4, LiBHEt3 ...
Examples.
WCl6 + LiBHEt3 + PR3 ------> WH6(PR3)3
PPh3
H
Cl
Ir
Ph3P
Cl
Ph3P

LiAlH4

PPh3
H
H
Ir
Ph3P
H
Ph3P

In some cases, complexes with BH4 or AlH4 entities may be obtained

when NaBH4 or NaBH4 are used.
PR3
H
Cl

Ir

Cl NaBH4 H

PR3
Ir

H
R3P

H
H

R3P

PR3
BH2 :L

Ir

H
L

R3P

+ H3B:L

(3) From H2

LnM + H2
16e
Ln M
Ph3P
Ph3P

OC
Ph3P

Rh
16e

Ir
16e

PPh3
Cl

PPh3
Cl

R + H2

Ln M

Ph3P

Ru
16e

PPh3
Cl

or

LnM

18e

L nM

H
H

+ R-H

16e

H
+ H H

Ph3P
Ph3P

PPh3

Rh

18e

Cl
H

+ H H

OC
Ph3P

PPh3
Cl

PPh3

Ir

18e

H
Cl
PPh3

+ H H

Cl

Ru

Ph3P
18e H H

PPh3
Cl

:NEt3 Cl
Ph3P

- HNEt3Cl

PPh3
Ru
16e

PPh3
H

Me
Me

Me

Me
Me

+ 6 H2 + 3 PMe2Ph

Me

WH6(PMe2Ph)3 + 6 CH4
18e
Me

Zr
Me

H
Zr

+ 2 H2

+ 2 CH4

M CH3 + H H

M H + H CH3

What are the likely intermediates or transition states?

H
(a) M R + H H

H
M

M H + H R

R
H
(b) M R + H H

H
M R

M H + H R

Me
Me

Me

Me

+ 6 H2 + 3 PMe2Ph

Me
Me

WH6(PMe2Ph)3 + 6 CH4
18e
Me

Zr
Me

H
Zr

+ 2 H2

+ 2 CH4

M CH3 + H H

M H + H CH3

What are the likely intermediates or transition states?

H
(a) M R + H H

H
M

M H + H R

R
H
(b) M R + H H

H
M R

Answer: (b)
W(VI) and Zr(IV)
Can not be
oxidized

M H + H R

(4) From ligands

Cl
Ph3P

PPh3
PPh3
Ru
Cl

+ NaOCHMe2 + PPh3
Ph3P
Ph3P

Q1. M-Cl + NaOCHMe2

M-H

PPh3
PPh3
Ru
H
H

+ NaCl +

how?

Q2. Can you use NaOH, NaOMe, NaOEt?

Q3. If NaOCDMe2, or NaOCH(CD3)2 were used, what is the
product?

Q1
Cl
Ph3P

PPh3
PPh3
Ru
+ NaOCHMe2 + PPh3
Cl
PPh3
PPh3
Ru
OCHMe2

Cl
Ph3P

Ph3P

Me2CHO

Ph3P
Ph3P

Cl
Ph3P

Ph3P
+ PPh3

Ph3P

PPh3
PPh3
Ru

Cl

NaOCHMe2

Cl

PPh3
PPh3
Ru
H

PPh3
PPh3
Ru
H
H

PPh3
PPh3
Ru
H

PPh3
PPh3
Ru
H

C
Ph3P

PPh3
PPh3
Ru
H
H

Q2
Any RO- with -H
should work.
Therefore NaOMe,
NaOEt will give the
same product.
-H is incorporated
to M.
Q3
NaOCD(CH3)2 =>
RuD2(PPh3)4
NaOCH(CD3)2 =>
RuH2(PPh3)4

PEt3
Cl

Pt

PEt3

CH2CH3

Cl

PEt3

Fe

OC
Ph3P

Pt

how?

PEt3

Cl

+ LiCH2CH2CH2CH3

Fe

OC
Ph3P

+
H

LiBu
LiCl
Fe
OC
Ph3P

detailed mechamism?

PEt3
Cl

PEt3

Pt CH2CH3

Cl

Pt H

PEt3

Cl

PEt3
PEt3

PEt3

Pt CH2

Pt CH2

PEt3

how?

Cl

CH2

Fe

OC
Ph3P

Cl

PEt3

CH2

+ LiCH2CH2CH2CH3

Pt

Cl
PEt3

CH2
H

Fe

OC
Ph3P

PEt3
CH2

+
H

LiBu
LiCl
Fe
OC
Ph3P

detailed mechamism?

Ph3P
Ph3P

H
Ir

PPh2
Cl

H
Ph3P

Ir
PPh3

PPh2
Cl

C. Chemical properties of M-H complexes

(1) Acidic and hydridic LnM-H
Hydridic hydride: H- donor, e.g.
NaH

Na+ + H-

Acidic hydride: H+ donor, e.g.

HCl

H+ + Cl-

What about a transition metal hydride complexes?

LnM-H can be acidic or hydridic ! Examples:
+
M

Ph3P
Ph3P

H
PPh3
PPh3
Ru

H
H

hydridic M-H !
M+ + H +

+ Ph3C+ BF4- Ph3P

Ph3C-H

Ph3P

PPh3 BF4
PPh3
Ru
H

M- + H +

H
OC Co
CO

CO
CO

Acidic M-H !

CO CO

pKa = 8.3

+ H+

OC Co
CO

(ii)FactorsinfluencinghydridicandacidicpropertiesofMH:
LnM

M-H-

M-H+

PropertiesofMHaredependentontheedensityonM.
Ingeneral,increaseinelectronrichnessofmetalcenter,will
>decreaseacidiccharacters
>increasehydridiccharacters

Exercises.
For each of the following pairs, which one is more acidic, which one is
more hydridic?
(a) H-Co(CO)4 vs H-Co(CO)3(PPh3)

(b) H-Co(CO)3(PMe3) vs H-Co(CO)3(PPh3)

(c)

CpRu(CO)2H vs CpOs(CO)2H

For each of the following pairs, which one is more acidic, which one is
more hydridic?
(a) H-Co(CO)4 vs H-Co(CO)3(PPh3)
H-Co(CO)4 is more acidic.
H-Co(CO)3(PPh3) is more hydridic.
Because PPh3 is more e- donating.

(b) H-Co(CO)3(PMe3) vs H-Co(CO)3(PPh3)

H-Co(CO)3(PMe3) is more hydridic.
H-Co(CO)3(PPh3) is more acidic.
Because PMe3 is more e- donating..
(c)

CpRu(CO)2H vs CpOs(CO)2H
CpRu(CO)2H is more acidic.
CpOs(CO)2H is more hydridic.
Because Os complexes are more e- rich.

General trends:
- pKa generally decreases as you move down a column
- pKa generally increases as you move to the right across the
transition series
- electron donating substituents decrease pKa values

(2) Chemical reactions

a. Deprotonation: reactions with nucleophiles (bases)

H + B:

M
e.g.

M- + BH+

WH6(PMe3)3 + NaH ------> Na[WH5(PMe3)3] + H2

OsH4(PR3)4 + NaH ---------> Na[OsH3(PR3)4] + H2

b. Reactions with electrophiles.

+ E+

M+ + E-H

e.g.
WH6(PMe3)3 + HBF4 + 3 MeCN ----->
[WH2(MeCN)3(PR3)3]2+ + H2

C. Insertion reactions

H +A

M
e.g.

H
OC

Mn

OC

CO
CO

+ CH2N2

CO

Cp2Zr

Cp2Zr

Cl
H

H
H

+ CH2=CH-R

+ 2 CH2=O

C. Insertion reactions

H +A

e.g.

H
OC

Mn

OC

CO
CO

CH2
+ CH2N2

CO

Cp2Zr

Cp2Zr

OC

Mn

OC

CO
CO

CO

Cl
H

H
H

+ CH2=CH-R

+ 2 CH2=O

Cp2Zr

Cp2Zr

Cl
CH2 CH R
H
CH2
H
O
O

CH2
H

Summary of reactivity of M-H