Metallaborane chemistry. Part I. Oxidative-insertion reactions of dicarbaundecaborane and metalladicarbaundecaborane species with zerovalent nickel, palladium, and platinum complexes

Abstract

Reaction of [Pt(PEt₃)₃], [Pt(PMe₃)₂(trans-stilbene)], [Pt(PMe₂Ph)₄], [Ni(1,5-C₈H₁₂)₂], [Ni(PEt₃)₂(1,5-C₈H_l2)], and [Pd(CNBu^t)₂] with closo-2,3-Me₂-2,3-C₂B₉H₉ affords the closo-metallacarbaboranes 1,1-L₂-2,4-Me₂-1,2,4-MC₂B₉H₉(M = Pt, L = PEt₃, PMe₃, or PMe₂Ph; M = Ni, L₂= 1,5-C₈H₁₂ or L = PEt₃; M = Pd, L = Bu^tNC). A single-crystal X-ray diffraction study of the metallacarbaborane obtained from [Pt(PMe₂Ph)₄] confirms the structural identity of the complex. Treatment of 1-(η-C₅H₅)-1,2,4-CoC₂B₈H₁₀ with [Pt(PEt₃)₂(trans-stilbene)] leads to a related insertion reaction to form 1-(η-C₅H₅)-8,8-(Et₃P)₂-1,2,7,8-CoC₂PtB₈H₁₀. An analogous reaction occurs with [Ni(1,5-C₈H₁₂)₂] to form a less-stable CoC₂NiB₈H₁₀ species.