Unexpected Formation of Early Late Heterobimetallic Complexes from Transition Metal Frustrated Lewis Pairs

Reaction of transition metal “frustrated” Lewis pair compounds of the type [Cp2Zr(Me)(OC(CF3)2CH2PtBu2)] with the low valent platinum species [Pt(norbornene)3] leads to the unexpected formation of a heterobimetallic species [Cp2Zr{Pt(Me)}(OC(CF3)2CH2PtBu2)]. Single crystal X-ray analysis reveals an unusual T-shaped geometry at the platinum center, with a relevant C–Pt–P angle of 163.3(3)°. Treatment of this compound with PMe3 yields [Pt(PMe3)4] and regenerates the zirconium precursor. Treatment with [(Et2O)2H][B(C6F5)4] protonates off the methyl ligand to give an ether adduct at platinum. Analogous observations are made with titanium–platinum species. We propose the chemistry is best rationalized as a formal insertion of Pt(0) into a Zr–C or Ti–Cl bond.