Reactivity of Lewis Basic Platinum Complexes Towards Fluoroboranes

We herein report detailed investigations into the interaction of Lewis acidic fluoroboranes, for example BF2Pf (Pf=perfluorophenyl) and BF2ArF (ArF=3,5-bis(trifluoromethyl)phenyl), with Lewis basic platinum complexes such as [Pt(PEt3)3] and [Pt(PCy3)2] (Cy=cyclohexyl). Two presumed Lewis adducts could be identified in solution and corresponding secondary products of these Lewis adducts were characterized in the solid state. Furthermore, the concept of frustrated Lewis pairs (FLP) was applied to the activation of ethene in the system [Pt(BPf3)(CH2CH2)(dcpp)] (dcpp=1,3-bis(dicyclohexylphosphino)propane; Pf=perfluorophenyl). Finally, DFT calculations were performed to determine the interaction between the platinum-centered Lewis bases and the boron-centered Lewis acids. Additionally, several possible mechanisms for the oxidative addition of the boranes BF3, BCl3, and BF2ArF to the model complex [Pt(PMe3)2] are presented.