Synthesis, Structure, and Reactivities of Iminosulfane- and Phosphane-Stabilized Carbones Exhibiting Four-Electron Donor Ability
Synthesis, Structure, and Reactivities of Iminosulfane- and Phosphane-Stabilized Carbones Exhibiting Four-Electron Donor Ability
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具有四电子供体能力的亚氨基硫烷和膦稳定碳的合成、结构和反应性
DOI：
10.1002/chem.201502166
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
Takayoshi Fuji
中科院分区：
文献类型：
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作者：
Tomohito Morosaki;Wei-Wei Wang;Shigeru Nagase;Takayoshi Fuji
合成了亚氨基硫烷（磷烷）碳（0）衍生物（iSPC; Ar 3 P →C <$SPh 2（NMe）; Ar=Ph（1），4-MeOC 6 H4（2），4-（Me 2N）C6 H4（3）），并对其结构进行了表征。Carbone 3是第一个由磷和硫配体稳定的热稳定和水解稳定的碳。DFT计算揭示了1 -3的电子结构，在碳中心有两个孤对电子。第一和第二质子亲和力值理论上计算分别在286.8-301.1和189.6-208.3 kcal mol-1的范围内。 循环伏安法测试表明，BChCs的HOMO能级为3>2> 1，其中3的HOMO能级高于BChCs的HOMO能级。这些孤对电子的反应性通过C-二金化和C-质子-金化络合物证明。这些结果是磷和硫稳定的碳作为四电子供体的第一个实验证据。此外，碳的盐酸盐与Ag_2O反应，得到相应的AgI配合物。所得银（I）碳酮络合物可用作碳酮转移剂。该合成方案也可用于对水分敏感的碳物种。
Iminosulfane(phosphane)carbon(0) derivatives (iSPCs; Ar3P→C←SPh2(NMe); Ar=Ph (1), 4‐MeOC6H4(2), 4‐(Me2N)C6H4(3)) have been successfully synthesized and the molecular structure of3characterized. Carbone3is the first thermally and hydrolytically stable carbone stabilized by phosphorus and sulfur ligands. DFT calculations reveal the electronic structures of1–3, which have two lone pairs of electrons at the carbon center. First and second proton affinity values are theoretically calculated to be in the range of 286.8–301.1 and 189.6–208.3 kcal mol−1, respectively. Cyclic voltammetry measurements reveal that the HOMO energy levels follow the order of3>2>1and the HOMO of3is at a higher energy than those of bis(chalcogenane)carbon(0) (BChCs). The reactivities of these lone pairs of electrons are demonstrated by the C‐diaurated and C‐proton‐aurated complexes. These results are the first experimental evidence of phosphorus‐ and sulfur‐stabilized carbones behaving as four‐electron donors. In addition, the reaction of hydrochloric salts of the carbones with Ag2O gives the corresponding AgIcomplexes. The resulting silver(I) carbone complexes can be used as carbone transfer agents. This synthetic protocol can also be used for moisture‐sensitive carbone species.