Abstract
AbstractThe 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.B. L. Barnett and C. Krüger, J. Cryst. Mol. Struct., im Druck. The ylid is bonded to the nickel through the C‐atom with resulting hybridization from sp2 towards sp3.
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