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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >New 13-vertex metallacarborane sandwich compounds; synthetic and structural studies
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New 13-vertex metallacarborane sandwich compounds; synthetic and structural studies

机译：新的13顶点金属碳硼烷夹心化合物;综合和结构研究

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摘要

Reduction of 1,12-closo-C2B10H12 followed by reaction with the appropriate metal halide and metathesis with either [K(18-crown-6)]Br or [BTMA] Cl ([BTMA] = [C6H5CH2N(CH3)(3)](+)) affords isolable salts of the supraicosahedral metallacarborane sandwich anions [4,4'-M-(1,10-closo-C2B10H12)(2)](n-) in moderate to good yield. Compounds prepared are [BTMA][4,4'-Co-(1,10-closo-C2B10H12)(2)] (1), [K(18-crown-6)][4,4'-Co-(1,10-closo-C2B10H12)(2)] (2), [K(18-crown-6)](2)[4,4'-Ni-(1,10-closo-C2B10H12)(2)] (3), [K(18-crown-6)](2)[4,4'-Fe-(1,10-closo-C2B10H12)(2)] (4), [BTMA] 2[4,4'-Fe-(1,10-closo-C2B10H12)(2)] (5) and [K(18-crown-6)](2)[4,4'-Ti-(1,10-closo-C2B10H12)(2)] (6). Oxidation of the iron(II) species 4 and 5 with FeCl3 in THF generates the iron(III) analogues [K(18-crown-6)][4,4'-Fe-(1,10-closo-C2B10H12)(2)] (7) and [BTMA][4,4'-Fe-(1,10-closo-C2B10H12)(2)] (8), respectively. All diamagnetic compounds were characterised spectroscopically and the structures of 1, 3, 4, 6, 7 and 8 were established by single crystal X-ray diffraction. All anions have the anticipated cluster structures with two docosahedral 13-vertex cages joined at the central metal atom (the common degree-six vertex 4). Carbon atoms occupy the degree-four vertex 1 and the degree-five vertex 10. B-11 NMR spectroscopy suggests the anions have, on the NMR timescale, C-2h symmetry in solution at room temperature, consistent with free rotation, or at least substantial libration, of cage units about the long molecular axis. In the solid state the relative conformations of the two cages may be rationalised by simple bonding arguments, the single exception being the conformation of 4, in which both cages are subject to directional B-H center dot center dot center dot K+ interactions to the [K(18-crown-6)](+) counterion. The salts 3, 6 and 7 also show B-H center dot center dot center dot K+ interactions but involving one cage only.
机译：还原1,12-closo-C2B10H12，然后与适当的金属卤化物反应，并与[K（18-crown-6）] Br或[BTMA] Cl复分解（[BTMA] = [C6H5CH2N（CH3）（3） ]（+））以中等至良好的收率提供表面上二十面体金属碳硼烷夹心阴离子[4,4'-M-（1,10-closo-C2B10H12）（2）]（n-）的可分离盐。制备的化合物为[BTMA] [4,4'-Co-（1,10-closo-C2B10H12）（2）]（1），[K（18-crown-6）] [4,4'-Co-（ 1,10-closo-C2B10H12）（2）]（2），[K（18-crown-6）]（2）[4,4'-Ni-（1,10-closo-C2B10H12）（2）] （3），[K（18-crown-6）]（2）[4,4'-Fe-（1,10-closo-C2B10H12）（2）]（4），[BTMA] 2 [4,4 '-Fe-（1,10-closo-C2B10H12）（2）]（5）和[K（18-crown-6）]（2）[4,4'-Ti-（1,10-closo-C2B10H12 ）（2）]（6）。在THF中用FeCl3氧化铁（II）4和5生成铁（III）类似物[K（18-crown-6）] [4,4'-Fe-（1,10-closo-C2B10H12）（ 2）]（7）和[BTMA] [4,4'-Fe-（1,10-closo-C2B10H12）（2）]（8）。通过光谱表征所有抗磁性化合物，并通过单晶X射线衍射确定1、3、4、6、7和8的结构。所有阴离子都具有预期的簇结构，在中心金属原子（共同度为6的顶点4）处连接了两个十二面体的13顶点笼。碳原子占据4级顶点1和5级顶点10。B-11NMR光谱表明，在NMR时标上，阴离子在室温下在溶液中具有C-2h对称性，与自由旋转一致，或至少与笼单元围绕长分子轴的充分释放。在固态状态下，两个笼的相对构象可以通过简单的键合参数来合理化，唯一的例外是4的构象，其中两个笼都受到与[K（ 18-crown-6）]（+）抗衡离子。盐3、6和7还显示出B-H中心点中心点中心点K +相互作用，但仅涉及一个笼。

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