Synthesis, structural characterization, and reactivity of Group 4 metallacarboranes bearing the ligand [H2C(C5Me4)(C2B9H10)]3-

Abstract

A new organic-inorganic hybrid ligand H(2)C(C(5)Me(4)H)(C(2)B(10)H(11)) (2) has been prepared. A selective deboration reaction with piperidine in ethanol resulted in the isolation of [Me(3)NH][H(2)C(C(5)Me(4)H)(C(2)B(9)H(11))] (3). An amine-elimination reaction of 3 with [Zr(NMe(2))(4)] produced a neutral metal-amide complex [η(5):η(5)-H(2)C(C(5)Me(4))(C(2)B(9)H(10))]Zr(NMe(2))(NHMe(2)) (4). The double-ring-opening reaction of 4 with tetrahydrofuran (THF) afforded [η(5):η(5)-H(2)C(C(5)Me(4))(C(2)B(9)H(10))]Zr (OCH(2)CH(2)CH(2)CH(2))(2)N(CH(3))(2) (5). Treatment of the trianionic salt of 3 with [MCl(4)(thf)(2)] gave complexes [{η(5):η(5)-H(2)C(C(5)Me(4))(C(2)B(9)H(10))}M(μ-Cl)(2)][Li(thf)(2)] (M=Zr (6), Hf (7)). Reaction of 6 with LiCH(2)TMS generated the ionic species [{η(5):η(5)-H(2)C(C(5)Me(4))(C(2)B(9)H(10))}Zr(CH(2)TMS)(2)][Li(thf)(3)] (9). Interaction of complex 6 with KCH(2)(NMe(2))-o-C(6)H(4) led to the formation of the neutral metal alkyl complex [η(5):η(5)-H(2)C(C(5)Me(4))(C(2)B(9)H(10))]Zr[σ:σ-CH(2)(NMe(2))-o-C(6)H(4)] (10). All complexes have been fully characterized by various spectroscopic techniques and elemental analyses. Some were further confirmed by single-crystal X-ray analyses.