Synthesis and cluster structure distortions of biscarborane dithiol, thioether, and disulfide
Synthesis and cluster structure distortions of biscarborane dithiol, thioether, and disulfide
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DOI：
10.1039/d3dt04289h
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发表时间：
2024-01-31
影响因子：
4
通讯作者：
Peryshkov，Dmitry V.
中科院分区：
文献类型：
--
作者：
Riffle，Jared R.;Hemingway，Tyler M.;Peryshkov，Dmitry V.
报道了C，C-双碳硼烷{邻-C2B10}2簇合物--硫醇、硫醚和二硫化物的第一个含硫衍生物的合成和结构表征。双碳硼烷二硫醇(1-HS-C2B10H10)2具有很长的簇内碳-碳键长度1.858(3)ä，这归因于碳硼烷团簇中孤对硫醇与空位分子轨道之间的广泛相互作用。具有不同反阳离子的双去质子化二碳硼基二硫代阴离子(1-S-C2B10H10)22−的结构特征是团簇内更长的碳-碳键长度为2.062(10)ä和短的碳-硫键长度为1.660(7)ä，两者都表明电子密度从硫原子显著离域到团簇中。
The synthesis and structural characterization of the first sulfur-containing derivatives of the C,C-biscarborane {ortho-C2B10}2 cluster – thiol, thioether, and disulfide – are reported. The biscarboranyl dithiol (1-HS-C2B10H10)2 exhibits an exceedingly long intracluster carbon–carbon bond length of 1.858(3) Å, which is attributed to the extensive interaction between the lone pairs of the thiol groups and the unoccupied molecular orbital of the carborane cluster. The structures of the doubly deprotonated biscarboranyl dithiolate anion (1-S-C2B10H10)22− with various counter cations feature an even longer carbon–carbon bond length of 2.062(10) Å within the cluster along with a short carbon–sulfur bond of 1.660(7) Å, both indicative of significant delocalization of electron density from the sulfur atoms into the cluster.