F. Heydenreich, A. Mollbach, G. Wilke
1972
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Influential Citations
72
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Journal
Israel Journal of Chemistry
Abstract
The Stevens rearrangement of the triarylphosphorusylids R3 P=CHR′ (III) (R′ = H, CH3, C2 H5) to diarylbenzylphosphines (V) is catalyzed by nickel complexes (e.g., (COD)2 Ni (I)). Attempts to prepare trimesitylphosphine-methylene result in direct formation of dimesityl (mesitylmethyl) phosphine (XII) — the first recorded direct Stevens rearrangement of a phosphorusylid. Phosphorusylids react with nickeltetracarbonyl without rearrangement to give complexes of the type R3P=CHa · Ni(CO)3 (XIV). The structure of XIV has been established by the IR and NMR spectra and confirmed by an X-ray structural determination.1 The ylid is bonded to the nickel through the C-atom with resulting hybridization from sp2 towards sp3.