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Synthesis,Structure, and Reactivities of Iminosulfane‐ and Phosphane‐Stabilized Carbones Exhibiting Four‐Electron Donor Ability
Authors:Tomohito Morosaki  Dr. Wei‐Wei Wang  Prof. Shigeru Nagase  Prof. Takayoshi Fujii
Affiliation:1. Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba 275‐8575 (Japan);2. Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606‐8103 (Japan)
Abstract: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 of 3 characterized. Carbone 3 is the first thermally and hydrolytically stable carbone stabilized by phosphorus and sulfur ligands. DFT calculations reveal the electronic structures of 1 – 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 of 3 > 2 > 1 and the HOMO of 3 is 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 AgI complexes. 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.
Keywords:carbones  density functional calculations  donor–  acceptor systems  electronic structure  gold
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