Synthesis and reactivity of organometallic nickel(II) complexes obtained by oxidation of nickel(0) complexes with halogenated organic compounds

Abstract

Reaction of the complexes [Ni(dpb)₂][dpb = 1,4-bis(diphenylphosphino)butane] and [Ni(dpp)₂][dpp = 1,3-bis(diphenylphosphino)propane] with RCOX (R = Ph or Et; X = Cl or Br) in benzene, in molar ratio 1 : 1, at room temperature, produces nickel(II)-acyl complexes. The spontaneous decomposition of these species produces nickel(II) dihalogenodiphosphino-complexes, nickel(0) monocarbonyldiphosphino-complexes, and benzophenone or diethyl ketone.

Reaction of [Ni(dpb)₂] with PhBr gives [NiBr(Ph)(dpb)], which undergoes ready carbonylation with CO in benzene to give benzoyl bromide.