Abstract
Carbene complexes of group VI B metal carbonyls react with nucleophiles by two alternate pathways, depending on the nucleophilicity of the reagent: substitution of one CO ligand or addition to the carbene carbon atom. Reactions of carbene complexes with phosphines, amines and acetylenes are discussed to illustrate the selectivity of such reactions. A second electrophilic center at the carbene moiety, such as in siloxycarbene complexes, leads to different products. With electrophiles methoxy (organyl) carbene complexes react by cleavage of the methoxy group to yield carbyne complexes. Depending on the nature of the ligand “trans” to the carbene ligand, neutral or cationic carbyne complexes are obtained. Amino (methoxy) carbene complexes (two different nucleophilic centers) yield amino (halo) carbene complexes on treatment with boron trihalides.
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