Synthesis and structure of N-acetyliminosulfane-stabilized carbone C(SPh2NC(O)Me)2

Abstract

N-acetyliminosulfane-stabilized carbone bis(acetyliminosulfane)carbon( 0) C(SPh2NC(O)Me)2 has been successfully synthesized by deprotonation of the corresponding salt [HC(SPh2NC(O)Me)2]ClO4. The molecular structures of [HC(SPh2NC(O)Me)2]ClO4 and C(SPh2NC(O)Me)2 were characterized using 1 H-and 13 C-NMR and Xray crystallographic analyses. Density functional theory calculations revealed that the electronic structure of C(SPh2NC(O)Me)2 has two lone pairs of electrons at the central carbon atom. The first and second proton affinities (PAs) of C(SPh2NC(O)Me)2 (PA(1): 271.3 kcal mol -1 ; PA(2): 181.2 kcal mol -1 ) are smaller than those of (methyliminosulfane)carbone(0) C(SPh2NMe)2 (PA(1): 278.8 kcal mol -1 ; PA(2): 182.2 kcal mol -1 ). C(SPh2NC(O)Me)2 was also compared with previously prepared sulfur-stabilized carbones.

Carbones – A Classification on the Magnetic Criterion

“…) δ( 13 C=O) 149.2(145.5) [32] ; d C=O = 1.185 Å (1.200 Å) [32] ; CÀ CÀ O: 174.9°(174.6) [32] . et al [33] synthesized and structurally assigned a variety of push, pull-and push, push-allenes (28)(29)(30)(31)(32)(33)(34) which, in a first step, have been calculated and analyzed as the afore standing heteroanalogues. Structures are given in Scheme 6, geometry and 13 C chemical shifts are collected in Table 4.…”

“…Next the phosphorus,sulfur-(PÀ CÀ S) 4 and sulfur,sulfur-stabilized carbones (SÀ CÀ S) 5 have been studied; changes in structure and electron distribution to the carbodiphosphoranes 1 were expected. In case of sulfur, Fujii and coworkers [10,[26][27][28][29][30] synthesized (Scheme 3) S II (18), S IV (17, 20) carbones and the mixed analogues (19, 21); the PÀ CÀ S II stabilized carbone 16 was synthesized and structurally assigned in the research groups of Bertrand and Baceiredo. [31] Geometry and NMR parameters of the representatives have been calculated as for the aforementioned carbodiphosphoranes 1.…”