Department of Chemistry and Center of Novel Functional Molecules, The Chinese University of Hong Kong, Shatin, NT, Hong Kong, China.
Chem Asian J. 2011 Feb 1;6(2):628-37. doi: 10.1002/asia.201000638. Epub 2010 Dec 10.
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.
一种新的有机-无机杂化配体 H(2)C(C(5)Me(4)H)(C(2)B(10)H(11))（2）已被制备。在乙醇中与哌啶的选择性去硼反应导致分离出[Me(3)NH][H(2)C(C(5)Me(4)H)(C(2)B(9)H(11))]（3）。3 与[Zr(NMe(2))(4)]的胺消除反应生成中性金属酰胺配合物[η(5):η(5)-H(2)C(C(5)Me(4))(C(2)B(9)H(10))]Zr(NMe(2))(NHMe(2))（4）。4 与四氢呋喃（THF）的双环开环反应得到[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）。用 3 的三阴离子盐与[MCl(4)(thf)(2)]处理得到配合物[{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））。6 与 LiCH(2)TMS 反应生成离子物种[{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）。6 与 KCH(2)(NMe(2))-o-C(6)H(4)的相互作用导致中性金属烷基配合物[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）的形成。所有配合物均通过各种光谱技术和元素分析进行了充分表征。一些通过单晶 X 射线分析进一步证实。
