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Chapter 14 Organometallic Compounds
Chapter 14 Organometallic Compounds
14.1
Organometallic Compounds Organometallic Nomenclature
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
CH3CH2MgCH2CH3 CH3MgI
Diethylmagnesium Methylmagnesium
iodide
+ – – +
R X R M
organometallics are a
source of nucleophilic
carbon
CH3F CH3Li
Organolithium Compounds
It is an oxidation-reduction reaction:
carbon is reduced and metal is oxidized.
diethyl
ether
Br + 2Li Li + LiBr Li•
R ••Li R• + •• X
–
35°C
(95-99%)
Grignard Reagents
diethyl
ether •
Mg+
Br + Mg MgBr R •Mg+ R• + •• X
• X– –
• •
35°C
(95%)
Forbidden Groups
– R + R H CH3CH2CH2CH2Li + H2O
H
• OR'
+ –• ••
M • •• M • OR'
••
Example
MgBr + CH3OH
+ CH3OMgBr
(100%)
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
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%)
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
(62%)
Example
O
H2C CHLi + CH
CHCH CH2
OH
(76%)
14.9
Retrosynthetic Analysis
C C
OH OH
Example CH3
Retrosynthetic Analysis of Alcohols
C CH2CH3
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–
(90%)
(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
H H H CH2CH3
Carbene
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
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
(Benzene)tricarbonylchromium
Example
Ferrocene
Fe
14.14
Homogeneous Catalytic 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
Step 5: Hydride migrates from Rh to carbon. Step 6: Active form of the catalyst is regenerated.
Olefin Metathesis
The reaction is generally catalyzed a transition metal Ring-opening metathesis is used as a method of
complex. Typically Ru, W, or Mo are used. Shown polymerization.
below is Grubbs’ catalyst.
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
Al(CH2CH3)3 Al(CH2CH3)3
Ziegler found that oligomerization was Natta found that polymerization of propene
affected differently by different transition under Ziegler's conditions gave mainly
metals. Some gave oligomers with 6-18 isotactic polypropylene. This discovery made
carbons, others gave polyethylene. it possible to produce polypropylene having
useful properties.
Al(CH2CH3)3 Al(CH2CH3)3
The ethylene oligomers formed under The polyethylene formed under Ziegler's
Ziegler's conditions are called linear -olefins conditions is called high-density polyethylene
and have become important industrial and has, in many ways, more desirable
chemicals. properties than the polyethylene formed by
free-radical 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
etc.
H2C CH2
+
Zr CH2CH2CH2CH2CH3