Boranediyl- and Diborane(4)-1,2-diyl-Bridged Platinum A-Frame Complexes

Chemistry. 2020 Jul 14;26(39):8518-8523. doi: 10.1002/chem.202001168. Epub 2020 Jun 17.

Abstract

Diplatinum A-frame complexes with a bridging (di)boron unit in the apex position were synthesized in a single step by the double oxidative addition of dihalo(di)borane precursors at a bis(diphosphine)-bridged Pt0 2 complex. While structurally analogous to well-known μ-borylene complexes, in which delocalized dative three-center-two-electron M-B-M bonding prevails, theoretical investigations into the nature of Pt-B bonding in these A-frame complexes show them to be rare dimetalla(di)boranes displaying two electron-sharing Pt-B σ-bonds. This is experimentally reflected in the low kinetic stability of these compounds, which are prone to loss of the (di)boron bridgehead unit.

Keywords: EDA-NOCV; bonding; boron; oxidative addition; platinum.