Binuclear complexes of nickel bridged by hydrocarbon ligands. Isocyanide insertion chemistry and amide formation by intramolecular coupling of acyl and imidoyl functionalities

Article abstract of DOI:10.1021/om00037a006

Ni(cod)(PMe₃)₂ and the o-, m-, and p-bromobenzyl bromides react, under appropriate conditions, to afford the binuclear complexes Ni₂(η₂-η³,η¹-CH ₂C₆H₄)Br₂(PMe₃) ₃ (1a-c) or Ni₂(μ₂-η¹,η¹-CH ₂C₆H₄)Br₂-(PMe₃) ₄ (2b,c). The reaction of the ortho η³-benzylic derivative 1a with isocyanides, CNR, has been investigated, and three different isomeric species have been identified for R = Bu^t. The CNC₆H₃-2,6-Me₂ insertion product, 4, reacts with CO to form a Ni(II)-vinyl complex 7 derived from the N-aryl-1-isoquinolone 8, which can be freed by hydrolytic cleavage of the Ni-vinyl bond.