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Chapter 11

Organometallic Compounds

Organic Chemistry 6th Edition

Paula Yurkanis Bruice

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Organometallic Compounds

An organic compound containing a carbon–metal bond

Organolithium compounds and organomagnesium compounds are two of the most common organometallic compounds

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Preparation of Organolithium Compounds

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Preparation of Organomagnesium Compounds

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Alkyl halides, vinyl halides, and aryl halides can all be used to form organolithium and organomagnesiumcompounds

However, these organometallic compounds cannot be prepared from compounds containing acidic groups (OH, NH2, NHR, SH, C=CH, CO2H)

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Coupling Reactions

Preparation of the Gilman reagent:

Example of carbon–carbon formation using the Gilman reaction:

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Gilman reagents can be used to prepare compounds that cannot be prepared by using nucleophilic substitution reactions:

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Gilman reagents can replace halogens in compounds containing other functional groups:

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The Heck Reaction

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The Stille Reaction

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The Suzuki Coupling

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Mechanism of the Suzuki Coupling Reaction

Oxidative addition: Pd (0) to Pd (II):

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Hydroxide exchange:

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Transmetallation:

Reductive elimination:

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Mechanism of the Heck Coupling Reaction

Oxidative addition: Pd (0) to Pd (II):

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Complex formation:

Insertion:

complex

complex

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Elimination: Transstereochemistry

Regeneration of the catalyst: Undergoes oxidative addition to bromobenzene