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Synthesis, Electronic Structure, and Reactivities of Two‐Sulfur‐Stabilized Carbones Exhibiting Four‐Electron Donor Ability
Author(s) -
Morosaki Tomohito,
Iijima Ryo,
Suzuki Tsubasa,
Wang WeiWei,
Nagase Shigeru,
Fujii Takayoshi
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201700863
Subject(s) - lone pair , chemistry , protonation , deprotonation , sulfur , crystallography , proton , density functional theory , carbon fibers , proton affinity , electronic structure , stereochemistry , computational chemistry , molecule , organic chemistry , materials science , ion , physics , quantum mechanics , composite number , composite material
Bis(sulfane)carbon(0) (BSC; Ph 2 S→C←SPh 2 ( 1 )) is successfully synthesized by deprotonation of the corresponding protonated salt 1⋅ HTfO. The diprotonated salt 1⋅ (HTfO) 2 as the starting material can be also easily accessed by the deimination of iminosulfane(sulfane)carbon(0) (iSSC) ⋅ HBF 4 . 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 S II 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 I carbone complexes as carbone transfer agents are also reported.