Cationic,Methylene‐Bridged,Intramolecular Donor‐Acceptor Systems Based on Zirconium and Hafnium and Phosphino‐methanides |
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| Authors: | Martin Pieper Pauline Auer Sabrina Schwarzbich Franziska Kühn Beate Neumann Hans‐Georg Stammler Norbert W Mitzel |
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| Affiliation: | 1. Fakult?t für Chemie, Lehrstuhl für Anorganische Chemie und Strukturchemie (ACS), Centrum für molekulare Materien CM2, Universit?t Bielefeld, Bielefeld, Germany;2. +49‐521‐106‐6026 |
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| Abstract: | 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. |
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| Keywords: | Transition metals Phosphinomethanides Geminal Donor Acceptor Organometallic compound |
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