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Chapter 14

Organometallic Compounds

With electrons flowing from ethylene to zirconium, the ZrOCH3 bond weakens, the carbons of ethylene become positively polarized, and the methyl group migrates from zirconium to one of the carbons of ethylene. Cleavage of the ZrOCH3 bond is accompanied by formation of a bond between zirconium and one of the carbons of ethylene in step 3. The product of this step is a chain-extended form of the active catalyst, ready to accept another ethylene ligand and repeat the chain-extending steps. Before coordination polymerization was discovered by Ziegler and applied to propene by Natta, there was no polypropylene industry. Now, more than 1010 pounds of it are prepared each year in the United States. Ziegler and Natta shared the 1963 Nobel Prize in Chemistry: Ziegler for discovering novel catalytic systems for alkene polymerization and Natta for stereoregular polymerization. Well see more about ZieglerNatta polymerization in Chapter 27 when we examine the properties of synthetic polymers in more detail.

14.17 SUMMARY
Section 14.1

Organometallic compounds contain a carbonmetal bond. They are named as alkyl (or aryl) derivatives of metals.

CH3CH2CH2CH2Li
Butyllithium
Section 14.2

C6H5MgBr
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 C H
Methyllithium has a polar covalent carbonlithium bond.
Section 14.3 Section 14.4 Section 14.5

Li

HC

C Na

Sodium acetylide has an ionic bond between carbon and sodium.

See Table 14.3 See Table 14.3 Organolithium compounds and Grignard reagents are strong bases and react instantly with compounds that have OOH groups.

These organometallic compounds cannot therefore be formed or used in solvents such as water and ethanol. The most commonly employed solvents are diethyl ether and tetrahydrofuran.
Section 14.6 Section 14.7 Section 14.8 Section 14.9

See Tables 14.2 and 14.4 See Table 14.4 See Table 14.4 When planning the synthesis of a compound using an organometallic reagent, or indeed any synthesis, the best approach is to reason backward from the product. This method is called retrosynthetic analysis. Retrosynthetic analysis of 1-methylcyclohexanol suggests it can be prepared by the reaction of methylmagnesium bromide and cyclohexanone.

CH3 O OH
1-Methylcyclohexanol Cyclohexanone Methylmagnesium bromide

CH3MgBr

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Summary

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Section 14.10 Section 14.11 Section 14.12

See Tables 14.3 and 14.4 See Tables 14.3 and 14.4 Carbenes are species that contain a divalent carbon; that is, a carbon with only two bonds. One of the characteristic reactions of carbenes is with alkenes to give cyclopropane derivatives. Certain organometallic compounds resemble carbenes in their reactions and are referred to as carbenoids. Iodomethylzinc iodide (Section 14.11) is an example.

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Chapter 14

Organometallic Compounds

TABLE 14.4

CarbonCarbon Bond-Forming Reactions of Organometallic Reagents (Continued)

General equation and specic example O X R CR R W RCOH W R
Alcohol

Reaction (section) and comments Synthesis of alcohols using organolithium reagents (Section 14.7) Organolithium reagents react with aldehydes and ketones in a manner similar to that of Grignard reagents to produce alcohols.

RLi

1. diethyl ether 2. H3O

Alkyllithium

Aldehyde or ketone

Li

O X CH3CC(CH3)3

1. diethyl ether 2. H3O

OH W CC(CH3)3 W CH3
2-Cyclopropyl3,3-dimethyl2-butanol (71%)

Cyclopropyllithium

3,3-Dimethyl2-butanone

Synthesis of acetylenic alcohols (Section 14.8) Sodium acetylide and acetylenic Grignard reagents react with aldehydes and ketones to give alcohols of the type W CPCCOH. W

NaCPCH

O X RCR

1. NH3, 33C 2. H3O

OH W HCPCCR W R
Acetylenic alcohol

Sodium acetylide

Aldehyde or ketone

NaCPCH

O X CH3CCH2CH3

1. NH3,

33C

2. H3O

OH W HCPCCCH2CH3 W CH3
3-Methyl-1-pentyn-3-ol (72%)

Sodium acetylide

2-Butanone

Preparation of alkanes using lithium dialkylcuprates (Section 14.10) Two alkyl groups may be coupled together to form an alkane by the reaction of an alkyl halide with a lithium dialkylcuprate. Both alkyl groups must be primary (or methyl). Aryl and vinyl halides may be used in place of alkyl halides.

R2CuLi
Lithium dialkylcuprate

R CH2X
Primary alkyl halide

RCH2R
Alkane
diethyl ether

(CH3)2CuLi
Lithium dimethylcuprate

C6H5CH2Cl
Benzyl chloride

C6H5CH2CH3
Ethylbenzene (80%)

The SimmonsSmith reaction (Section 14.11) Methylene transfer from iodomethylzinc iodide converts alkenes to cyclopropanes. The reaction is a stereospecic syn addition of a CH2 group to the double bond.

R R2CCR2
Alkene

R R ZnI2
Zinc iodide

ICH2ZnI
Iodomethylzinc iodide
CH2I2, Zn(Cu) diethyl ether

diethyl ether

Cyclopropane derivative

Cyclopentene

Bicyclo[3.1.0]hexane (53%)

Section 14.13

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. Metallocenes are transition-metal complexes in which one or more of the ligands is a cyclopentadienyl ring. Ferrocene was the first metallocene synthesized; its electrostatic potential map opens this chapter. and ruthenium, can catalyze the hydrogenation of alkenes under homogeneous conditions.

Section 14.14 Organometallic compounds based on transition metals, especially rhodium

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Problems

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O CH CHCOH
H2 [(C6H5)3P]3RhCl

O CH2CH2COH
3-Phenylpropanoic acid (90%)

Cinnamic acid

When a single enantiomer of a chiral catalyst is used, hydrogenations can be carried out with high enantioselectivity.
Section 14.15

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

2R2C

CR 2

Metallocarbene catalyst

R2C

CR2

R 2C

CR 2

Among other applications olefin metathesis is useful in the synthesis of cyclic alkenes, the industrial preparation of propene, and in polymerization.
Section 14.16

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
14.15

Write structural formulas for each of the following compounds. Specify which compounds qualify as organometallic compounds. (a) Cyclopentyllithium (e) Sodium carbonate (b) Ethoxymagnesium chloride (f) Benzylpotassium (c) 2-Phenylethylmagnesium iodide (g) Lithium diisopropylamide (d) Lithium divinylcuprate Suggest appropriate methods for preparing each of the following compounds from the starting material of your choice. (a) CH3CH2CH2CH2CH2MgI (b) CH3CH2C CMgI (c) CH3CH2CH2CH2CH2Li (d) (CH3CH2CH2CH2CH2)2CuLi Which compound in each of the following pairs would you expect to have the more polar carbonmetal bond? (a) CH3CH2Li or (CH3CH2)3Al (b) (CH3)2Zn or (CH3)2Mg (c) CH3CH2MgBr or HC CMgBr Write the structure of the principal organic product of each of the following reactions: (a) 1-Bromopropane with lithium in diethyl ether (b) 1-Bromopropane with magnesium in diethyl ether (c) 2-Iodopropane with lithium in diethyl ether (d) 2-Iodopropane with magnesium in diethyl ether (e) Product of part (a) with copper(I) iodide (f) Product of part (e) with 1-bromobutane (g) Product of part (e) with iodobenzene (h) Product of part (b) with D2O and DCl (i) Product of part (c) with D2O and DCl ( j) Product of part (a) with formaldehyde in diethyl ether, followed by dilute acid (k) Product of part (b) with benzaldehyde in diethyl ether, followed by dilute acid

14.16

14.17

14.18