Synthesis, Structure, and Reactivities of Iminosulfane- and Phosphane-Stabilized Carbones Exhibiting Four-Electron Donor Ability.

Iminosulfane(phosphane)carbon(0) derivatives (iSPCs; Ar3PCSPh2(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 189.6-208.3kcalmol(-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 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.