Morosaki Tomohito, Iijima Ryo, Suzuki Tsubasa, Wang Wei-Wei, Nagase Shigeru, Fujii Takayoshi
Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba, 275-8575, Japan.
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto, 606-8103, Japan.
Chemistry. 2017 Jun 27;23(36):8694-8702. doi: 10.1002/chem.201700863. Epub 2017 May 5.
Bis(sulfane)carbon(0) (BSC; Ph S→C←SPh (1)) is successfully synthesized by deprotonation of the corresponding protonated salt 1⋅HTfO. The diprotonated salt 1⋅(HTfO) as the starting material can be also easily accessed by the deimination of iminosulfane(sulfane)carbon(0) (iSSC)⋅HBF . Density functional theory calculations revealed the peculiar electronic structure of 1, which has two lone pairs of electrons at the central carbon atom. The largest proton affinities (PA(1): 297.5 kcal mol ; PA(2): 183.7 kcal mol ) and the highest energy levels of the HOMOs (HOMO: -4.89 eV; HOMO-1: -5.02 eV) for 1 among the two-sulfur-stabilized carbones clearly indicate the strong donor ability of carbon center stabilized by two S ligands. The donating ability of these lone pairs of electrons is demonstrated by the C-diaurated and C-proton-aurated complexes, which provide the first experimental evidence for two-sulfurstabilized carbones behaving as four-electron donors. Furthermore, the syntheses and application of Ag carbone complexes as carbone transfer agents are also reported.
通过相应的质子化盐1·HTfO的去质子化成功合成了双（硫烷）碳（0）（BSC；PhS→C←SPh（1））。作为起始原料的双质子化盐1·（HTfO）也可以通过亚氨基硫烷（硫烷）碳（0）（iSSC）·HBF的脱亚氨基反应轻松获得。密度泛函理论计算揭示了1的特殊电子结构，其中心碳原子有两对孤对电子。在双硫稳定的碳烯中，1具有最大的质子亲和能（PA（1）：297.5 kcal mol；PA（2）：183.7 kcal mol）和最高的HOMO能级（HOMO：-4.89 eV；HOMO-1：-5.02 eV），这清楚地表明了由两个S配体稳定的碳中心具有很强的给体能力。这些孤对电子的给体能力通过C-二金化和C-质子金化配合物得到证明，这为双硫稳定的碳烯作为四电子给体提供了首个实验证据。此外，还报道了Ag碳烯配合物作为碳烯转移剂的合成及应用。
