Synthesis, Structural Characterization, and Reactivity of Group 4 Metallacarboranes Bearing the Ligand [H2C(C5Me4)(C2B9H10)]3−
作者： Dongmei Liu , Hao Shen , Yaorong Wang , Yuepeng Cai , Zuowei Xie
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摘要: The new inorganic/organic hybrid π ligand [Me2C(C5H4)(C2B9H10)]3− was prepared via a selective deboration of Me2C(C5H5)(C2B10H11) with piperidine in ethanol. Treatment its sodium salt MCl4(THF)2 gave the mixed-sandwich complexes [{η5:η5-Me2C(C5H4)(C2B9H10)}MCl2][Na(DME)3] (M = Zr (4), Hf (5)). Complex 4 reacted C5H5Na, KCH2Ph, or NaNH(C6H3-2,6-Pri2) to afford {[η5:η2-Me2C(C5H4)(C2B9H10)]Zr(η5-C5H5)(μ-Cl)}{Na(DME)2} (7), [{η5:η5-Me2C(C5H4)(C2B9H10)}ZrCl(CH2C6H5)][Na(DME)3] (8), [η5:η5-Me2C(C5H4)(C2B9H10)]Zr(NHC6H3Pri2)(THF) (9), respectively. Both 7 and 8 were stable, no NaCl elimination observed upon heating toluene solution. In presence excess MAO (methylalumoxane), 4, 5, very active catalysts for ethylene polymerization. All fully characterized by various spectroscopic techniques elemental analyses. Some further confirmed single-crystal X-ray
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