Chapter 14

14.1
Organometallic Compounds Organometallic Nomenclature

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Metal is the parent

Li H2C CHNa 14.2

Carbon-Metal Bonds
in
Cyclopropyllithium Vinylsodium
Organometallic Compounds

CH3CH2MgCH2CH3 CH3MgI
Diethylmagnesium Methylmagnesium
iodide

Polarity of Bonds Polarity of Bonds

+ – – +
R X R M

organometallics are a
source of nucleophilic
carbon

CH3F CH3Li
 Organolithium Compounds

normally prepared by reaction of alkyl halides

with lithium
14.3
R X + 2Li R Li + LiX
Preparation of Organolithium Compounds
(same for Ar—X)

It is an oxidation-reduction reaction:
carbon is reduced and metal is oxidized.

Examples Electron Bookkeeping

diethyl
ether
•
(CH3)3CCl + 2Li (CH3)3CLi + LiCl R X + Li • [R X] – + Li+
–10°C
(75%)

diethyl
ether
Br + 2Li Li + LiBr Li•
R ••Li R• + •• X
–
35°C
(95-99%)

Grignard Reagents

prepared by reaction of alkyl halides

with magnesium
14.4
Preparation of R X + Mg RMgX
Organomagnesium Compounds:
Grignard Reagents (same for Ar—X)

Diethyl ether is most often used solvent.

Tetrahydrofuran is also used.
Examples Electron Bookkeeping
diethyl
ether •
• •
Cl + Mg MgCl R X + Mg • [R X] – + Mg+
–10°C
(96%)

diethyl
ether •
Mg+
Br + Mg MgBr R •Mg+ R• + •• X
• X– –
• •
35°C
(95%)

Order of Reactivity Forbidden Groups

certain groups cannot be present in

I > Br > Cl >> F the solvent

RX > ArX the halide from which the Grignard reagent

is prepared
the substance with which the Grignard
reagent reacts

Forbidden Groups

Anything with an OH, SH, or NH group

therefore:
14.5
- cannot use H2O, CH3OH, CH3CH2OH, Organolithium and Organomagnesium
etc. as solvents Compounds as Brønsted Bases
- cannot prepare Grignard reagent from
substances such as HOCH2CH2Br, etc.
 Brønsted basicity Example

– R + R H CH3CH2CH2CH2Li + H2O
H

• OR'
+ –• ••
M • •• M • OR'
••

Grignard reagents (M = MgX) and

organolithium reagents (M = Li) are strong CH3CH2CH2CH3 + LiOH
bases.
(100%)

Example

MgBr + CH3OH

+ CH3OMgBr

(100%)

Acetylenic Grignard Reagents

are prepared by an acid-base reaction

14.6
CH3CH2MgBr + HC CH
Synthesis of Alcohols Using
stronger acid
Grignard Reagents

CH3CH3 + HC CMgBr
weaker acid
 Grignard reagents act as nucleophiles
Grignard reagents react with:
toward the carbonyl group

+ diethyl formaldehyde to give primary alcohols

– R R C
C ether
aldehydes to give secondary alcohols
MgX O •• • O • + MgX
• •• •–
•• ketones to give tertiary alcohols
H3O+
esters to give tertiary alcohols
Two-step sequence
R C
gives an alcohol as
the isolated product. • OH
• ••

Grignard reagents react with: Grignard reagents react with formaldehyde

formaldehyde to give primary alcohols H

H + H diethyl
– R R C H
C ether
•O•
+
MgX O •• • •• •– MgX
••

H3O+ H

Product is a R C H
primary
• OH
alcohol. • ••

Example
Grignard reagents react with:

Mg
Cl MgCl formaldehyde to give primary alcohols
diethyl
aldehydes to give secondary alcohols
ether
H
C O
H

H3O+
CH2OH CH2OMgCl

(64-69%)
 Example
Grignard reagents react with aldehydes
Mg
H CH3(CH2)4CH2Br CH3(CH2)4CH2MgBr
H diethyl
– R + R' diethyl
C ether R C R' ether H3C

MgX O •• • O • + MgX C O
• •• •–
••
H
H3O+ H H3O+
CH3(CH2)4CH2CHCH3 CH3(CH2)4CH2CHCH3
Product is a R C R'
secondary alcohol. OH OMgBr
• OH
• •• (84%)

Grignard reagents react with: Grignard reagents react with ketones

formaldehyde to give primary alcohols R"

R" + R' diethyl
aldehydes to give secondary alcohols – R R C R'
C ether
ketones to give tertiary alcohols •O• +
MgX O •• • •• •– MgX
••

H3O+ R"

Product is a R C R'
tertiary alcohol.
• OH
• ••

Example

Mg
CH3Cl CH3MgCl
diethyl 14.7
ether O
Synthesis of Alcohols
Using Organolithium Reagents

Organolithium reagents react with

aldehydes and ketones in the same
HO CH3 ClMgO CH3
H3O+ way that Grignard reagents do.

(62%)
 Example
O

H2C CHLi + CH

1. diethyl ether 14.8

Synthesis of Acetylenic Alcohols
2. H3O+

CHCH CH2

OH
(76%)

Using Sodium Salts of Acetylenes Using Acetylenic Grignard Reagents

NaNH2 CH3(CH2)3C CH + CH3CH2MgBr

HC CH HC CNa
NH3 diethyl ether
O HO C CH
1. NH3 CH3(CH2)3C CMgBr + CH3CH3
HC CNa + 1. H2C O
2. H3O+
2. H3O+
(65-75%)
CH3(CH2)3C CCH2OH
(82%)

Retrosynthetic Analysis of Alcohols

14.9
Retrosynthetic Analysis

Retrosynthetic analysis is the process by

which we plan a synthesis by reasoning C
backward from the desired product (the
OH
"target molecule").

Step 1 Locate the carbon that bears the

hydroxyl group.
 Retrosynthetic Analysis of Alcohols Retrosynthetic Analysis of Alcohols

C C

OH OH

Step 2 Disconnect one of the groups

attached to this carbon.

Example CH3
Retrosynthetic Analysis of Alcohols
C CH2CH3

MgX There are two OH

other
possibilities.

C Can you see

them? CH3MgX
O
O
What remains is the combination of Grignard
reagent and carbonyl compound that can be C CH2CH3
used to prepare the alcohol.

Synthesis
Mg, diethyl ether
CH3Br CH3MgBr

O
14.10
1. C CH2CH3 Alkane Synthesis Using
Organocopper Reagents
2. H3O+
CH3

C CH2CH3

OH
 How?
Lithium Dialkylcuprates
The alkyllithium first reacts with the copper(I)
Lithium dialkylcuprates are useful synthetic halide,
reagents. R Li R Li+
They are prepared from alkyllithiums and a
copper(I) halide. Cu I Cu I–

2RLi + CuX R2CuLi + LiX then a second molecule of the alkyllithium

reacts with the alkylcopper species formed in
the first step.
[customary solvents are diethyl ether and
tetrahydrofuran (THF)] R Li+
R Li
R Cu R Cu –

Example: Lithium Dimethylcuprate

Lithium Diorganocuprates are Used to
Form C—C Bonds
(CH3)2CuLi + CH3(CH2)8CH2I

R2CuLi + R'X R R' + RCu + LiX diethyl ether

Ar2CuLi + R'X Ar R' + ArCu + LiX CH3(CH2)8CH2CH3

(90%)

Primary alkyl halides work best (secondary and

tertiary alkyl halides undergo elimination).

Example: Lithium Diphenylcuprate Vinylic Halides Can be Used

(C6H5)2CuLi + CH3(CH2)6CH2I
(CH3CH2CH2CH2)2CuLi + Br
diethyl ether

diethyl ether
CH3(CH2)6CH2C6H5

(99%)
CH2CH2CH2CH3

(80%)
 Aryl Halides Can be Used

(CH3CH2CH2CH2)2CuLi + I 14.11
An Organozinc Reagent
for
diethyl ether Cyclopropane Synthesis

CH2CH2CH2CH3

(75%)

Example
Iodomethylzinc Iodide

Formed by reaction of diiodomethane with

zinc that has been coated with copper CH2CH3 CH2CH3
(called zinc-copper couple) CH2I2, Zn/Cu
H2C C
diethyl ether CH3
Cu CH3
CH2I2 + Zn ICH2ZnI (79%)

Reacts with alkenes to form cyclopropanes

Reaction with alkenes is called the
Simmons-Smith reaction.

Stereospecific syn-Addition Stereospecific syn-Addition

CH3CH2 CH2CH3 CH3CH2 H

C C C C
H H H CH2CH3

CH2I2, Zn/Cu diethyl ether CH2I2, Zn/Cu diethyl ether

CH3CH2 CH2CH3 CH3CH2 H

H H H CH2CH3
 Carbene

Name given to species that contains a

divalent carbon (carbon with two bonds
and six electrons).
14.12 ••
Carbenes and Carbenoids C
Br Br

dibromocarbene

Carbenes are very reactive:

-normally cannot be isolated and stored;
-are intermediates in certain reactions.

Generation of Dibromocarbene Generation of Dibromocarbene

Br ••
– •• C
• OC(CH ) –
Br C H + • 3 3 Br Br
+ Br
••

Br

Br Br
– •• –
Br C• • + H OC(CH3)3 Br C ••
••

Br Br

Carbenes React with Alkenes

to Give Cyclopropanes

Br 14.13
KOC(CH3)3
+ CHBr3 Transition-Metal Organometallic Compounds
(CH3)3COH Br

(75%)

:CBr2 is an intermediate.
Reaction is stereospecific syn addition
 Introduction 18-Electron Rule

The number of ligands attached to a metal

Many organometallic compounds derived
from transition metals have useful properties.
Typical transition metals are iron, nickel,
chromium, platinum, and rhodium.
will be such that the sum of the electrons
brought by the ligands plus the valence
electrons of the metal equals 18.
When the electron-count is less than 18,
metal is said to be coordinatively unsaturated
and can take on additional ligands.
18-Electron rule is to transition metals as
the octet rule is to second-row elements.

(Benzene)tricarbonylchromium
Example

Ni is in Group 10, so:

CO Ni has 10 valence Cr
electrons. OC CO
OC Ni CO Each CO uses 2 CO
electrons to bond to Ni.
CO
4 CO’s contribute 8 Cr has the electron configuration [Ar]4s23d4.
Nickel carbonyl valence electrons. Cr has 6 valence electrons.
10 + 8 = 18 Each CO uses 2 electrons to bond to Cr.
3 CO’s contribute 6 valence electrons.
Benzene uses its 6  electrons to bind to Cr.

Ferrocene

Fe
14.14
Homogeneous Catalytic Hydrogenation

Fe2+ is in Group 8, but is in the +2 oxidation state, Wilkinson’s Catalyst

so it contributes 8-2 = 6 electrons.
Each cyclopentadienide anion contributes 6  electrons.
Total 6 + 6 + 6 = 18
Organometallic compounds with cyclopentadienide
ligands are called metallocenes.
 Wilkinson’s Catalyst Mechanism of Homogeneous Hydrogenation

Ni, Pt, Pd, and Rh can act as heterogeneous

catalysts in the hydrogenation of alkenes. Steps 1 and 2: Catalyst is converted to the active form.
However, tris(triphenylphosphine)rhodium chloride - (C6H5)3P
+ H2
was found to be soluble in organic solvents. then
Cl
This catalyst was developed by Sir Geoffrey P(C6H5)3 Cl
H P(C6H5)3
Wilkinson, who received a Nobel Prize in 1973. Rh Rh
(C6H5)3P P(C6H5)3 (C6H5)3P H
P(C6H5)3 then
- (C6H5)3P + H2
(C6H5)3P Rh Cl
This is the active
form of the catalyst.
P(C6H5)3
Wilkinson's Catalyst

Mechanism of Homogeneous Hydrogenation Mechanism of Homogeneous Hydrogenation

Step 3: Alkene bonds to rhodium through  electrons. Step 4: Rhodium-alkene complex rearranges.

H P(C6H5)3
Cl
H P(C6H5)3
Rh Cl
(C6H5)3P H Rh
(C6H5)3P CH2CH2CH3

CH2=CHCH3
Rhodium-alkene complex

Mechanism of Homogeneous Hydrogenation Mechanism of Homogeneous Hydrogenation

Step 5: Hydride migrates from Rh to carbon. Step 6: Active form of the catalyst is regenerated.
 Olefin Metathesis

In crossed-olefin metathesis, one alkene is converted

to a mixture of two new alkenes.
14.15
Olefin Metathesis

The reaction is reversible, and regardless of

whether we start with propene or a 1:1 mixture of
ethylene and 2-butene, the same mixture is
obtained.

Olefin Metathesis Ring-Opening Metathesis

The reaction is generally catalyzed a transition metal
complex. Typically Ru, W, or Mo are used. Shown
below is Grubbs’ catalyst.
Ring-opening metathesis is used as a method of
polymerization.
Usually, it is applied when ring opening creates a
relief of strain, as in some bicyclic alkenes.

Ethylene Oligomerization

n H2C CH2
14.16
Al(CH2CH3)3
Ziegler-Natta Catalysis of
Alkene Polymerization
CH3CH2(CH2CH2)n-2CH CH2
The catalysts used in coordination
polymerization are transition-metal organic Triethylaluminum catalyzes the formation of
compounds. alkenes from ethylene.
These compounds are called ethylene
oligomers and the process is called
oligomerization.
 Karl Ziegler (1950) Giulio Natta

n H2C CH2 n H2C CHCH3

Al(CH2CH3)3 Al(CH2CH3)3

CH3CH2(CH2CH2)n-2CH CH2 polypropylene

Ziegler found that oligomerization was
affected differently by different transition
metals. Some gave oligomers with 6-18
carbons, others gave polyethylene.
Natta found that polymerization of propene
under Ziegler's conditions gave mainly
isotactic polypropylene. This discovery made
it possible to produce polypropylene having
useful properties.

Karl Ziegler (1950) Karl Ziegler (1950)

n H2C CH2 n H2C CH2

Al(CH2CH3)3 Al(CH2CH3)3

CH3CH2(CH2CH2)n-2CH CH2 CH3CH2(CH2CH2)n-2CH CH2

The ethylene oligomers formed under
Ziegler's conditions are called linear -olefins
and have become important industrial
chemicals.
The polyethylene formed under Ziegler's
conditions is called high-density polyethylene
and has, in many ways, more desirable
properties than the polyethylene formed by
free-radical polymerization.

Ziegler-Natta Catalysts Ziegler-Natta Catalysts

Early Ziegler-Natta catalysts Early Ziegler-Natta catalyst

were a combination of TiCl4 were a combination of TiCl4
and (CH3CH2)2AlCl, or TiCl3 and (CH3CH2)2AlCl, or TiCl3
and (CH3CH2)3Al. Cl and (CH3CH2)3Al.
Zr
Currently used Ziegler-Natta Currently used Ziegler-Natta
catalyst combinations include a Cl catalyst combinations include a
metallocene such as metallocene such as
bis(cyclopentadienyl)zirconium bis(cyclopentadienyl)zirconium
dichloride. dichloride.
 Ziegler-Natta Catalysts Mechanism of Coordination Polymerization

The metallocene is used in combination with a

promoter such as methyl alumoxane (MAO). Cl MAO Cl
Zr Zr
Cl CH3
O—Al—O—Al
– Cl–
CH3 CH3
n
This is the active +
Zr CH3
form of the catalyst.

Mechanism of Coordination Polymerization Mechanism of Coordination Polymerization

CH3 CH2CH2CH3
+ +
Zr Zr
CH2 H2C CH2 CH2
H2C H2C

+ +
Zr CH2 CH2 CH3 H2C CH2 Zr CH2 CH2 CH3

+ +
Zr CH3 Zr CH2CH2CH2CH2CH3

Mechanism of Coordination Polymerization

etc.
H2C CH2

+
Zr CH2CH2CH2CH2CH3