Addition of Phosphorus-Hydrogen and Arsenic-Hydrogen Bonds to Vinyl Isocyanide.

摘要

Addition of diphenylphosphine or diphenylarsine to vinyl isocyanide catalysed by potassium t-butoxide gives the liquid 2-diphenylphosphinoethyl (I) or diphenylarsinoethyl isocyanide (II). However, a similar addition of phenylphosphine to vinyl isocyanide in tetrahydrofuran solution gives 4,5-dihydro-3-phenyl-1,3-azaphosphole rather than phenylphosphinediylbis(ethyl isocyanide). Reactions of compounds (I) and (II) with tetracarbonylnorbornadienechromium at room temperature give the yellow polymetal derivatives (Ph2E.CH2CH2NC)4Cr3(CO)12 (E=P or As) rather than the simple monometal derivatives (PH2E.CH2CH2NC)Cr(CO)4, in accord with the relative orientations of the two lone pairs in the ligand (I) or (II). (Author)