Organometallic compounds, 1,4-addition carbene complexes

The majority of gold(I) carbene complexes are pure organometallic compounds and the are out of the scope of this work. Some halide or triphenylphosphine carbene complexes are known and they will be considered here. Nucleophilic addition of alcohols or amines to gold-coordinated isocyanides is one of the best-established methods to obtain gold carbene derivatives. The reaction of H[Au(CN)2] with propene oxide and estirene oxide yields (cyano)carbene complexes (380) avoiding the intermediate step.2257 A cyclic carbene compound is obtained by reaction of a dinuclear isocyanide with amine (Scheme 32).2258... 

In this chapter, we have considered just a few types of reactions of organometallic compounds, principally the replacement of CO by other ligands and the reactions involved in syntheses of carbene and carbyne complexes. Additional types of reactions will be discussed in Chapter 14. We conclude this chapter with two examples of how spectral data may be used in the characterization of organometallic compounds. Further examples can be found in the problems at the end of this chapter and in Chapter 14. 

The reactivity of metal-silylene complexes is more limited than the reactivity of carbene complexes. The cationic base-stabilized ruthenium-silylene complex in Equation 13.37 does not react with olefins or alkynes to undergo [2-1-2] addition reactions. However, a related complex did undergo [2-1-2] addition reactions with isocyanates, as shown in Equation 13.46. Other reactions of silylene complexes are distinct from those of carbene complexes or those of other conventional organometallic compounds. For example, the reaction of the silylene hydride with an acetylene generates a p-silylvinylarene complex... 

Addition of anionic Fischer carbene complexes, of their CS2 adducts and of an anionic thiocarbyne complex to cationic organometallic Lewis acids and to coordinated, unsaturated hydrocarbons gives novel hydrocarbon bridged heterodimetallic compounds. Oxidative addition of halocarbyne complexes to zerovalent platinum and palladium complexes provides a synthesis of carbido bridged complexes. 

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