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.

Two‐sulfur‐stabilized carbones: the presence of a “second” lone pair on a coordinated atom significantly enhances the electron‐donating ability of the central carbon in carbones. The strongest electron‐donating ability of bis(sulfane)carbon(0) (BSC) among the two‐sulfur‐stabilized carbones was demonstrated by the generation of diprotonated salt BSC⋅H2+. The C‐digold(I) complexes of two‐sulfur‐stabilized carbones provide the first experimental proof of their four‐electron‐donating ability. More information can be found in the Full Paper by T. Fujii et al. on page 8694.

No abstract