Chapter 12

Organometalli
c Compounds

Paula Yurkanis Bruice

University of California,
Santa Barbara
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Organometallic Compounds in
Nature

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Organometallic Compounds in
Nature

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Carbon is an Electrophile

Carbon is an electrophile when it is attached to

an electron-withdrawing group.
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Carbon is a Nucleophile

Carbon is a nucleophile when it is attached to a metal.

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Many Metals Can Be Used to Make

Organometallic Compounds

An organometallic compound contains a carbonmetal bond.

Organomagnesium and organolithium compounds
are two of the most common organometallic compounds.
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Nomenclature

Name the alkyl group, then the metal.

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Organolithium Compounds

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Organomagnesium Compounds

Organomagnesium compounds are also called Grignard reagents.

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The Synthesis of a Grignard Reagent is

Carried Out in an Ether Solvent

The solvent provides electrons so magnesium can complete its octet.

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Organomagnesium and Organolithium

Compounds React as if They Were Carbanions

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Organomagnesium and Organolithium Compounds

Will React with a Proton of an Acidic Group

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How to Prepare
a Deuterated Hydrocarbon

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Transmetallation

An organometallic compound will undergo transmetallation (metal exchange)

if a less polar carbonmetal bond will be formed.

The more polar the carbonmetal bond,

the more reactive the organometallic compound.
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Organocuprates

Organocuprates are also called Gilman reagents.

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The Alkyl Group of an Organocuprate

Replaces a Halogen

A coupling reaction joins two CH-containing groups.

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The Configuration of the Double Bond

is Retained

Organocuprates can be used to prepare compounds

that cannot be prepared by using nucleophilic substitution reactions.
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Other Functional Groups

Can Be Present

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The Reaction of an Organocuprate

with Ethylene Oxide

The product has two more carbons than the alkyl group of the organocuprate.

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The Suzuki and Heck Reactions

(palladium-catalyzed coupling reactions)

Both reactions replace the halogen of a vinylic halide

or an aryl halide with a carbon-containing group.
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Suzuki and Heck Reactions

both reactions start by inserting a palladium

between the alkyl group and the halogen
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The Suzuki Reaction

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The Suzuki Reaction Couples a Vinylic or Aryl

Halide with an Organoboron Compound

the organoboron compound can be an

alkyl, alkenyl,or aryl group
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The Mechanism

The first step is oxidative addition.

The fourth step is transmetallation.
The last (fifth) step is a reductive elimination.
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Preparing Alkyl- and Alkenyl-Boron Compounds

(hydroboration of a terminal alkene or alkyne)

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Preparing an
Aryl-Organoboron Compound

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The Heck Reaction Couples a

Vinylic or Aryl Halide with an Alkene

The R group of the halide replaces a vinylic hydrogen.

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The Mechanism

High yields are obtained only if Z is an electron withdrawing group.

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Why High Yields Are Obtained if Z is an

Electron Withdrawing Group

the electron withdrawing group makes the carbon more electrophilic

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Alkene Metathesis
The double bond breaks and the fragments are rejoined.
Each new double bond is formed between
two sp2 carbons that were not previously joined.

attaching sp2 carbons to form new alkenes

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Alkene Metathesis

attaching sp2 carbons to re-form the reactant alkene

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Alkene Metathesis Requires

a Grubbs Catalyst

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Alkene Metathesis Forms

E and Z Isomers

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Two Different Alkenes Can Be Used as

Starting Materials in Alkene Metathesis

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Ring-Closing Metathesis

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Mechanism for Alkene Metathesis

Phase 1

The first phase creates two metal-containing intermediates.

In each intermediate, the metal is bonded to an sp2 carbon.
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Mechanism for Alkene Metathesis

Phase 2

In the second phase, each intermediate reacts with the starting material
to form a new alkene and the other metal-containing intermediate.
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Alkyne Metathesis

The preferred catalyst for alkyne metathesis is a Schrock catalyst

(a catalyst that contains molybdenum or tungsten).

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