Synthesis, Electronic Structure, and Reactivities of Two-Sulfur-Stabilized Carbones Exhibiting Four-Electron Donor Ability.
Bis(sulfane)carbon(0) (BSC; Ph2S→C←SPh2(1)) is successfully synthesized by deprotonation of the corresponding protonated salt 1⋅HTfO. The diprotonated salt 1⋅(HTfO)2as the starting material can be also easily accessed by the deimination of iminosulfane(sulfane)carbon(0) (iSSC)⋅HBF4. 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-1; PA(2): 183.7 kcal mol-1) 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 SIIligands. 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 AgIcarbone complexes as carbone transfer agents are also reported.
Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba, 275-8575, Japan.
Tomohito
T
Morosaki
Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba, 275-8575, Japan.
Ryo
R
Iijima
Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba, 275-8575, Japan.
Tsubasa
T
Suzuki
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto, 606-8103, Japan.
Wei-Wei
WW
Wang
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto, 606-8103, Japan.
Shigeru
S
Nagase
Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba, 275-8575, Japan.
Takayoshi
T
Fujii
carbones; density functional calculations; donor-acceptor systems; electronic structure; gold