C–X bond formation and cleavage in the reactions of the ditungsten hydride complex [W2(η5-C5H5)2(H)(μ-PCy2)(CO)2] with small molecules having multiple C–X bonds (X = C, N, O)

Abstract

Two molecules of C₂(CO₂Me)₂ or isocyanides could be added to the title hydride complex under mild conditions to give dienyl-[W₂Cp₂{μ-η¹,κ:η²-C(CO₂Me)C(CO₂Me)C(CO₂Me)CH(CO₂Me)}(μ-PCy₂)(CO)₂] (Cp = η⁵-C₅H₅), diazadienyl-[W₂Cp₂{μ-κ,η:κ,η-C{CHN(4-MeO–C₆H₄)}N(4-MeO–C₆H₄)}(μ-PCy₂)(CO)₂] or aminocarbyne-bridged derivatives [W₂Cp₂{μ-CNH(2,6-Me₂C₆H₃)}(μ-PCy₂){CN(2,6-Me₂C₆H₃)}(CO)]. In contrast, its reaction with excess (4-Me–C₆H₄)C(O)H gave the C–O bond cleavage products [W₂Cp₂{CH₂(4-Me–C₆H₄)}(O)(μ-PCy₂)(CO)₂] and [W₂Cp₂{μ-η:η,κ-C(O)CH₂(4-Me–C₆H₄)}(O)(μ-PCy₂)(CO)].