Reactions of low-valent metal complexes with fluorocarbons. Part XXI. Five-membered ring complexes from phosphine, arsine, and phosphite palladium (0) compounds

Abstract

Reaction of PdL₄[L = P(OPh)₃ or PMePh₂] with (CF₃)₂C:O affords complexes [graphic omitted]L₂; whereas when L = P(OMe)₃, P(OMe)₂Ph, or AsMe₂(CH₂C₆H₅), five-membered ring compounds [graphic omitted]L₂ are formed directly. Hexafluoroacetone reacts at higher temperatures with [graphic omitted](PMePh₂)₂ to form [graphic omitted](PMePh₂)₂. Also [graphic omitted]·L₂[L₂=(Ph₂PCH₂)₂] formed by treating [graphic omitted]-[P(OPh)₃]₂ with (Ph₂PCH₂)₂ reacts with (CF₃)₂C:O or (CF₃)₂C:NH to form analogous five-membered ring compounds. The mechanism of these reactions is discussed. Reaction of [graphic omitted][P(OMe)₃]₂ with ligands leads to the displacement of either one or both phosphite groups. Trifluoroiodomethane reacts with Pd[P(OMe)₃]₄ to form cis-Pd(CF₃)₂[P(OMe)₃]₂.