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

The intramolecular vicinal frustrated P/B Lewis pair (FLP) Mes2PCH2CH2B(C6F5)2 readily abstracts a methyl anion equivalent from dimethylzirconocene to give the salt [Cp2ZrCH3](+) [Mes2PCH2CH2B(CH3)(C6F5)2](-) that features phosphane coordination to the zirconium cation. The analogous reaction between this FLP and Cp*2Zr(CH3)2 yields the analogous salt that, however, features a methyl bridged ([Zr]···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.