Synthesis and characterisation of boranediyl- and diboranediyl-bridged diplatinum A-frame complexes

A series of boranediyl-bridged diplatinum A-frame complexes, [Pt2X2(μ-BY)(μ-dmpm)2] (X = Cl, Br, I; Y = aryl, alkyl, amino, halo; dmpm = bis(dimethylphosphino)methane), were synthesised by the twofold oxidative addition of BX2Y to [Pt2(nbe)2(μ-dmpm)2] (nbe = norbornene) or to the paddlewheel complex [Pt2(μ-dmpm)3]. Similarly, the addition of B2X2(NMe2)2 (X = Cl, Br) to [Pt2(nbe)2(μ-dmpm)2] provided access to the diborane-1,2-diyl-bridged A-frame complexes [Pt2X2(μ-1,2-B2(NMe2)2)(μ-dmpm)2]. X-ray crystallographic studies of these (BY)n-bridged complexes show structural trends depending on the steric demands of Y and the nature of X. Analysis of higher-order 31P NMR satellites provided information on JP-Pt and JPt-Pt coupling constants, the latter correlating with the PtPt distance. All (di)boranediyl complexes also proved unstable towards (successive) loss of the bridging "BY" unit(s), resulting in the formation of [Pt2X2(μ-dmpm)2].