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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes
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Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes

机译：C-二甲磺酰基-1,2-二氨基甲酰-clodo-十二硼烷的合成与还原

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摘要

Two C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes, 1-(BMes(2))-2-R-1,2-C2B10H10 (1, R = H, 2, R = Ph), were synthesised by lithiation of 1,2-dicarba-closo-dodecaborane and 1-phenyl-1,2-dicarba-closo-dodecaborane, respectively, with n-butyllithium and subsequent reaction with fluorodimesitylborane. These novel compounds were structurally characterised by X-ray crystallography. Compounds 1 and 2 are hydrolysed on prolonged exposure to air to give mesitylene and boronic acids 1-(B(OH)(2))-2-R-1,2-C2B10H10 (3, R = H, 4, R = Ph respectively). Addition of fluoride anions to 1 and 2 resulted in boryl-carborane bond cleavage to give dimesitylborinic acid HOBMes(2). UV absorption bands at 318-333 nm were observed for 1 and 2 corresponding to local pi-pi*-transitions within the dimesitylboryl groups while visible emissions at 541-664 nm with Stokes shifts of 11 920-16 170 cm(-1) were attributed to intra-molecular charge transfer transitions between the mesityl and cluster groups. Compound 2 was shown by cyclic voltammetry to form a stable dianion on reduction. NMR spectra for the dianion [2](2-) were recorded from solutions generated by reductions of 2 with alkali metals and compared with NMR spectra from reductions of 1,2-diphenyl-ortho-carborane 5. On the basis of observed and computed B-11 NMR shifts, these nido-dianions contain bowl-shaped cluster geometries. The carborane is viewed as the electron-acceptor and the mesityl group is the electron-donor in C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes.
机译：通过以下方法合成了两个C-二甲磺酰基-1,2-二氨基甲酰-clo-十二碳硼烷1-（BMes（2））-2-R-1,2-C2B10H10（1，R = H，2，R = Ph）分别用正丁基锂将1,2-二氨基甲酰-异十二烷硼烷和1-苯基-1,2-二氨基甲酰-十二硼烷锂化，然后与氟代二甲基异戊烷反应。通过X射线晶体学对这些新颖的化合物进行结构表征。长时间暴露于空气中会水解化合物1和2，得到均三甲苯和硼酸1-（B（OH）（2））-2-R-1,2-C2B10H10（3，R = H，4，R = Ph分别）。将氟阴离子添加到1和2中会导致硼基-碳氢键断裂，生成二聚二茂铁酸HOBMes（2）。在1和2处观察到在318-333 nm处的UV吸收带，对应于二聚三氟甲基内部的局部pi-pi *跃迁，而在541-664 nm处可见光发射，斯托克斯位移为11 920-16 170 cm（-1）。这归因于均基和簇基团之间的分子内电荷转移跃迁。通过循环伏安法显示化合物2在还原时形成稳定的二价阴离子。从用碱金属还原2生成的溶液中记录二价阴离子[2]（2-）的NMR光谱，并将其与从1，2-二苯基-邻甲碳烷5的还原中得到的NMR光谱进行比较。 B-11 NMR位移，这些亚氨基阴离子包含碗状簇的几何形状。在C-二异丁烯丙基-1，2-二氨基甲酰-氯-十二碳烷中，碳硼烷被视为电子受体，而均三甲苯基是电子给体。

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