title: Synthesis, Structure, and Reactivities of Iminosulfane- and Phosphane-Stabilized Carbones Exhibiting Four-Electron Donor Ability.
abstract: Iminosulfane(phosphane)carbon(0) derivatives (iSPCs; Ar3 P→C←SPh2 (NMe); Ar=Ph (1), 4-MeOC6 H4 (2), 4-(Me2 N)C6 H4 (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 Ag2 O gives the corresponding Ag(I) 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.
authors.affiliation: Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba 275-8575 (Japan).
authors.forename: Tomohito
authors.initials: T
authors.lastname: Morosaki
authors.affiliation: Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103 (Japan).
authors.forename: Wei-Wei
authors.initials: WW
authors.lastname: Wang
authors.affiliation: Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103 (Japan).
authors.forename: Shigeru
authors.initials: S
authors.lastname: Nagase
authors.affiliation: Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba 275-8575 (Japan). fujii.takayoshi@nihon-u.ac.jp.
authors.forename: Takayoshi
authors.initials: T
authors.lastname: Fujii
keywords: carbones; density functional calculations; donor-acceptor systems; electronic structure; gold