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DOI: 10.1055/s-2008-1067116
Application of Terminal Electrophilic Phosphinidene Complexes
Publication History
Publication Date:
19 June 2008 (online)
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Introduction
Phosphinidenes are phosphorus analogues of carbenes in which phosphorus is monovalent with an incomplete octet of electrons. Phosphinidene complexes readily react with alkenes, whereas free phosphinidenes do not react with alkenes. This indicates that the coordination of these unstable phosphorus compounds [¹] with metallic species enhances their stability as well as reactivity by increasing the electrophilicity of the phosphorus atom. A number of precursors like phosphiranes, [²] phospholenes, [²] norbornadienes, [³] 2H-azaphosphirene [4] and phosphirene [5] metal complexes are known to generate terminal phosphinidene complexes in situ via their thermal or photochemical decomposition. These phosphinidene complexes are short-lived intermediates and their existence is proved by trapping them with substituted alkenes, [6] acetylenes, [7] and organic nitriles [8] via cycloaddition reactions resulting in the formation of a variety of P-heterocycles. Recently, insertion of phosphinidene complexes into carbon-halogen bonds has been established, [9-¹¹] which affords a number of novel organophosphorus compounds.
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