Successive insertion of tetrafluoroethylene and CO and of tetrafluoroethylene and acetylenes into aryne–nickel(0) bonds 

Abstract

Aryne–nickel complexes [Ni(η²-C₆H₄)L₂] [L₂ = 2PEt₃ or dcpe; dcpe = (C₆H₁₁)₂PCH ₂CH₂P(C₆H₁₁)₂] and [Ni(η²-C₁₀H₆)(PEt₃) ₂] reacted readily with C₂F₄ to form the corresponding five-membered tetrafluoro-substituted nickelacycles [[upper bond 1 start]Ni(C₆H₄CF₂C[upper bond 1 end]F₂ -2)L₂] (L₂ = dcpe or 2PEt₃) and [[upper bond 1 start]Ni(2-C₁₀H₆CF₂C[upper bond 1 end]F ₂-3)(PEt₃)₂], respectively. The complex [[upper bond 1 start]Ni(C₆H₄CF₂C[upper bond 1 end]F₂ -2)(dcpe)] is very stable towards air, whereas the PEt₃ analogues react readily to give µ-aryloxo dimers. The naphthalene-based dimer [upper bond 1 start][{Ni(µ-2-OC₁₀H₆CF₂ [upper bond 1 end]CF₂-3)(PEt₃)}₂] has been structurally characterized. The complexes [[upper bond 1 start]Ni(C₆H₄CF₂C[upper bond 1 end]F₂ -2)L₂] insert CO into their aryl–nickel bonds to form six-membered acyl complexes [[upper bond 1 start]Ni{C(O)C₆H₄CF₂C[upper bond 1 end] F₂-2}L₂] (L₂ = dcpe or 2PEt₃) and, after CO-induced reductive elimination, 2,2,3,3-tetrafluoroindanone. The dcpe acyl complex has also been shown to undergo reaction with air to form the carboxylato complex [[upper bond 1 start]Ni{OC(O)C₆H₄CF₂C[upper bond 1 end] F₂-2}(dcpe)], whose structure has been confirmed by X-ray crystallography. Some insertions of acetylenes into the aryl–nickel bonds of [[upper bond 1 start]Ni(C₆H₄CF₂C[upper bond 1 end]F₂ -2)L₂] are also reported.

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