606

Chapter 14 Organometallic Compounds

14.15 SUMMARY
Section 14.1

Organometallic compounds contain a carbonmetal bond. Those derived from

main-group metals are named as alkyl or aryl derivatives of the metal.

CH3CH2CH2CH2Li or

C6H5MgBr or

Li

Butyllithium
Section 14.2

MgBr

Phenylmagnesium bromide

Carbon is more electronegative than metals, and carbonmetal bonds are polarized
so that carbon bears a partial to complete negative charge and the metal bears a
partial to complete positive charge.

H H

Li

HC

C Na

H
Methyllithium has a polar
covalent carbonlithium
bond.
Section 14.3

Sodium acetylide has an

ionic bond between carbon
and sodium.

Organolithium compounds and Grignard reagents are prepared by reaction

of the metal with an alkyl, aryl, or vinylic halide, usually in diethyl ether or
tetrahydrofuran as the solvent.

Br

Propyl bromide

diethyl ether

2Li

Li +

Lithium

Propyllithium
(78%)

Lithium
bromide

diethyl ether

Mg

Cl

MgCl
Magnesium

Benzyl chloride
Section 14.4

LiBr

Benzylmagnesium
chloride (93%)

Organolithium compounds and Grignard reagents are strong bases and react
instantly with compounds that have OH groups.

M H

H M O

Therefore, these organometallic reagents cannot be used in solvents such as water

or ethanol.
Section 14.5

The reaction of Grignard and organolithium reagents with carbonyl compounds

is one of the most useful methods for making carboncarbon bonds in synthetic
organic chemistry. These reagents react with formaldehyde to yield primary
alcohols, with aldehydes to give secondary alcohols, and with ketones to give
tertiary alcohols.

OH

CH3MgI

1. diethyl ether

Methylmagnesium
iodide
Section 14.6

2. H3O+

Butanal

2-Pentanol (82%)

The sodium salts of alkynes react with aldehydes and ketones in a manner
analogous to that of Grignard and organolithium reagents.

O
NaC CH +
Sodium
acetylide

OH
1. diethyl ether
2. H3O+

2-Butanone

3-Methyl-1-pentyn-3-ol
(72%)

14.15 Summary

Section 14.7

Retrosynthetic analysis of alcohols via Gignard and organolithium reagents begins

with a disconnection of one of the groups attached to the carbon that bears the
oxygen. The detached group is viewed as synthetically equivalent to a carbanion,
and the structural unit from which it is disconnected becomes the aldehyde or
ketone component.

CH3

OH
Section 14.8

CH3

Methylene transfer from iodomethylzinc iodide to alkene is called the Simmons

Smith reaction and converts alkenes to cyclopropanes.
CH2I2, Zn(Cu)
diethyl ether

2-Methyl-1-butene

1-Ethyl-1-methylcyclopropane (79%)

Stereospecific syn addition of a CH 2 group to the double bond occurs.

Section 14.9

Transition-metal complexes that contain one or more organic ligands offer a rich
variety of structural types and reactivity. Organic ligands can be bonded to a metal
by a bond or through its system. The 18-electron rule is a guide to the number
of ligands that may be attached to a particular metal.

Section 14.10

Lithium dialkylcuprates and diarylcuprates (R2CuLi and Ar2CuLi) are prepared

by the reaction of a copper(I) salt with two equivalents of the corresponding
organolithium reagent and undergo cross-coupling with primary alkyl halides and
aryl and vinylic halides.
diethyl ether

(CH3)2CuLi

Cl
Lithium dimethylcuprate
Section 14.11

Benzyl chloride

Ethylbenzene(80%)

Certain formulations of Pd(0) are catalysts for a number of useful carboncarbon

bond-forming processes represented by the general equation:
R'4Sn

RX

PdL2

Oxidative
addition

Reductive
elimination

R
R'ZnCl

PdL2
X

PdL2

R R' + PdL2

R'

R'B(OR")2
Transmetalation

The various methods are known as the Stille, Negishi, or Suzuki cross couplings
according to whether the organometallic component is a derivative of tin, zinc, or
boron, respectively. The Heck reaction accomplishes the same transformation but
uses an alkene as the reactant.
O

N C

Br

Pd(OAc)2

Ar3P

N C

OCH2CH3

OCH2CH3
1-Bromo-4-cyanobenzene
Section 14.12

Ethyl acrylate

Ethyl p-cyanocinnamate (70%)

Organometallic compounds based on transition metals, especially rhodium

and ruthenium, can catalyze the hydrogenation of alkenes under homogeneous
conditions.
O

OH
Cinnamic acid

H2
[(C6H5)3P]3RhCl

OH

3-Phenylpropanoic acid (90%)

607

608

Chapter 14 Organometallic Compounds

When a single enantiomer of a chiral catalyst is used, hydrogenations can be

carried out with high enantioselectivity.
Section 14.13

The doubly bonded carbons of two alkenes exchange partners on treatment with
transition-metal carbene complexes, especially those derived from ruthenium and
tungsten.

2R2C

Metallocarbene
catalyst

CR2

R2C

CR2 R2C

CR2

Among other applications olefin metathesis is useful in the synthesis of cyclic

alkenes, the industrial preparation of propene, and in polymerization.
Section 14.14

Coordination polymerization of ethylene and propene has the biggest economic

impact of any organic chemical process. ZieglerNatta polymerization is carried
out using catalysts derived from transition metals such as titanium and zirconium.
-Bonded and -bonded organometallic compounds are intermediates in
coordination polymerization.

PROBLEMS
14.20 Suggest appropriate methods for preparing each of the following organometallic compounds

from the starting material of your choice.

Li

MgBr

(a)

Li

(b)

(H2C=CH)2CuLi

(c)

(d)

14.21 Given the reactants in the preceding problem, write the structure of the principal organic

product of each of the following.

(a) Cyclopentyllithium with formaldehyde in diethyl ether, followed by dilute acid.
(b) tert-Butylmagnesium bromide with benzaldehyde in diethyl ether, followed by dilute
acid.
(c) Lithium phenylacetylide (C6H5C{ CLi) with cycloheptanone in diethyl ether, followed by dilute acid.
(d) Lithium divinylcuprate [(H2C CH)2CuLi] with 2-bromonaphthalene.
14.22 Predict the principal organic product of each of the following reactions:
O

(a)

NaC

(b)

CH3CH2Li

Br

2. H3O

1. Mg, THF
O
X
2. HCH

3. H3O
CH2I2

(d)

1. liquid ammonia

1. diethyl ether

(c)

CH

Zn(Cu)
diethyl ether

2. H3O