Reactions of dimethylzirconocene complexes with a vicinal frustrated P/B Lewis pair

The intramolecular vicinal frustrated P/B Lewis pair (FLP) Mes(2)PCH(2)CH(2)B(C6F5)(2) readily abstracts a methyl anion equivalent from dimethylzirconocene to give the salt [Cp2ZrCH3](+) [Mes(2)PCH(2)CH(2)B(CH3)(C6F5)(2)](-) that features phosphane coordination to the zirconium cation. The analogous reaction between this FLP and (Cp2Zr)-Zr-star(CH3)(2) yields the analogous salt that, however, features a methyl bridged ([Zr]center dot center dot center dot H3C-[B]) tight ion pair structure. Both these products were characterized by X-ray diffraction. They both undergo 1,2[ Zr+]/P addition to carbon dioxide. The [Cp2ZrCH3](+) containing compound also adds to benzaldehyde or to p-tolyl isocyanate to give the respective [Zr+]/P addition products which were characterized by X-ray diffraction.