Synthesis and decarbonylation chemistry of gallium phosphaketenes

Abstract

A series of gallium phosphaketenyl complexes supported by a 1,2-bis(aryl-imino)acenaphthene ligand (Dipp-Bian) are reported. Photolysis of one such species induced decarbonylation to afford a gallium substituted diphosphene. Addition of Lewis bases, specifically trimethylphosphine and the gallium carbenoid Ga(Nacnac) (Nacnac = HC[C(Me)N-(C₆H₃)-2,6-ⁱPr₂]₂), resulted in displacement of the phosphaketene carbonyl to yield base-stabilised phosphinidenes. In several of these transformations, the redox non-innocence of the Dipp-Bian ligand was found to give rise to radical intermediates and/or side-products.