Synthesis, Electronic Structure, and Reactivities of Two‐Sulfur‐Stabilized Carbones Exhibiting Four‐Electron Donor Ability

Abstract

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.

Carbodicarbene: geminal‐Bimetallic Coordination in Selective Manner

“…Both Pd and Au coordinate geminally at C1 of CDC with bond distance of 2.095(3) and 2.113(3) Å, respectively (Figure S5). The observed Au‐carbone bond length is comparable to literature values for gem ‐aurate supported by carbones (2.078 to 2.127 Å) [11a, 12b,c, 13a,c, 14, 15] . The bond angle of 84.97(10)° for Au‐C1‐Pd is slightly smaller than observed in 1 (89.25°).…”

Geminal Dianions Stabilized by Main Group Elements

“…206 Finally, 73 was used in the synthesis of triphenylphosphinomethylenyl-methanaminatodiphenylsulfur cation, which is further deprotonated to afford iminosulfane stabilized carbophosphorane 87. 207 143 Scheme 96: Reactivity of yldiide 73 toward a cyclic enolester, dichlorophenylborane and fluoromethanaminatodiphenylsulfur tetrafluoroborate.…”

“…Owing to the isolobal analogy between cationic gold(I) species and the proton, 404 407 The synthesis of monoaurated species of the type [bis(ylide)→AuCl] was extended to a broad variety of bis(ylides) (260, 262a,b, 264a,b). [321][322] Vicente demonstrated the synthetic utility of the Au(I)-complex 433 as an organometallic synthon which was then applied to obtain the 130→Au(acac) complex 439, the first isolated acetylacetonate Au-complex. 407 The presence of intramolecular base in ] supported by the P,S IV -mixed bis(ylide) 258 and the phosphallene 264b were prepared.…”

“…Extensive work regarding the selective synthesis of bis(ylide)-stabilized silver complexes was carried by Fujii's group since 2015. [321,322,414] 321 Silver to Au transmetalation was possible from these complexes, leading to the geminal diaurated coordination compounds [450][OTf], [451][OTf] and [452][OTf]. 321 The P,S to CuCl getting access to the synthesis of the neutral complex [130→CuCl] (494) that was isolated in 92% yield (Scheme 217).…”

Phosphine/Sulfoxide‐Supported Carbon(0) Complex

“…The P1−C1 bond length [1.6563(13) Å] in 2 is significantly shorter than in 1 [1.7190(15) Å] and the value remains slightly longer than those reported for CDPs (1.584–1.648 Å) . The S1−C1 bond length also undergoes significant shortening upon deprotonation [from 1.6539(15) Å in 1 to 1.5929(14) Å in 2 ], this value is the shortest S−C bond length reported to date in the sulfur‐stabilized carbone series (1.602–1.713 Å) ,. The S1−O1, S1−C16, and S1−C22 bond lengths get slightly longer (Δ S−X max=+0.02 Å).…”