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Synthesis, Structure, and Reactivities of Iminosulfane‐ and Phosphane‐Stabilized Carbones Exhibiting Four‐Electron Donor Ability
Author(s) -
Morosaki Tomohito,
Wang WeiWei,
Nagase Shigeru,
Fujii Takayoshi
Publication year - 2015
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.201502166
Subject(s) - chemistry , lone pair , sulfur , proton , carbon fibers , crystallography , electron , inorganic chemistry , molecule , organic chemistry , materials science , physics , quantum mechanics , composite number , composite material
Iminosulfane(phosphane)carbon(0) derivatives (iSPCs; Ar 3 P→C←SPh 2 (NMe); Ar=Ph ( 1 ), 4‐MeOC 6 H 4 ( 2 ), 4‐(Me 2 N)C 6 H 4 ( 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 Ag 2 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.