Cationic, Methylene‐Bridged, Intramolecular Donor‐Acceptor Systems Based on Zirconium and Hafnium and Phosphino‐methanides

A new access to cationic zirconium and hafnium compounds [L2MCH2PR2][MeB(C6F5)3] (L = Cp, Ind; R = iso‐Pr, tert‐Bu; M = Zr, Hf) exhibiting an intramolecular donor‐acceptor system was established by treating the precursors L2M(Me)CH2PR2 with B(C6F5)3 (BCF). Precursors 1–6 [L2M(Me)CH2PR2 with L = Cp, Ind; R = iso‐Pr, tert‐Bu; M = Zr, Hf] were fully characterized. The crystal structures of these compounds revealed large M–CH2–P bond angles with values of about 134° indicating the absence of interactions between the Lewis‐acid and Lewis‐base. The cationic compounds [L2MCH2PR2][MeB(C6F5)3] (7–12) were obtained by treatment of 1–6 with BCF. They were characterized by NMR spectroscopy, mass spectrometry, and elemental analyses; in H/D‐scrambling experiments with H2/D2 mixtures 7–12 disclosed their reactivity towards cleavage of hydrogen.