Synthesis and structural studies on thioimides, R2CNSR and sulfur diimides, R2CNSNCR2

Abstract

Reaction of Ph(2)C=O and py(2)C=O with Li[N(SiMe(3))(2)] and ArSCl (Ar = 2-O(2)NC(6)H(4), 2,4-(O(2)N)(2)C(6)H(3)) yielded Ph(2)C=NSAr (1a and 1b respectively) and py(2)C=NSAr (2a and 2b respectively). Reaction of fluorenone, C(12)H(8)C=O with Li[N(SiMe(3))(2)] and ArSCl under similar conditions afforded C(12)H(8)CNSAr (3a and 3b respectively). Whilst reaction of fluorenone with Li[N(SiMe(3))(2)] and SCl(2) in a 2 : 2 : 1 ratio afforded the sulfur-diimide, C(12)H(8)CNSNCC(12)H(8) (4), reaction of py(2)C=O with Li[N(SiMe(3))(2)] and SCl(2) under similar conditions afforded the thiazyl heterocycle [py(2)CNS]Cl (5) via intramolecular coordination. The structures of 1a, 1b, 2a, 2b, 3a, 3b and 4 are determined by X-ray diffraction. In the case of 4, bond lengths and DFT studies reveal greater π-delocalisation than in 1-3.

N,N’‐Diaryl‐Sulfurdiimides are Strongly Redox Tuned

“…Recently, −(Ar−NSN−Ar−) ∞ chain polymers have been reported, after a long unsuccessful search for such species [15] . Closely related to these achievements is the report of an unusual SDI that appears to be dominated by C aryl =N bonds and consequently possesses very long N−S bonds [16] . Cyclic diimides are known for all chalcogens, [1] and fused‐ring aryl‐1,2,5‐chalcogenadiazoles, 12 (Figure 2), are undoubtedly the largest of this very important and heavily studied class of SDIs.…”

“…[15] Closely related to these achievements is the report of an unusual SDI that appears to be dominated by C aryl = N bonds and consequently possesses very long NÀ S bonds. [16] Cyclic diimides are known for all chalcogens, [1] and fused-ring aryl-1,2,5-chalcogenadiazoles, 12 (Figure 2), are undoubtedly the largest of this very important and heavily studied class of SDIs. However, the electronic structures and resultant properties (especially luminescence) of such cyclic systems is dominantly a function of their modified aryl rings rather than the chalcogen atom and as such will not be further discussed in this article; [17] for the role of the chalcogen in 12 see ref.…”

The structure of the first stable monosubstituted sulfur diimide

“…The molecular structures and packing of materials with alternating double-bonded N and chalcogen atoms (including S) have been the subject of a number of papers [for examples, see Bagryanskaya et al (1997), Bagryanskaya (2009), Makarov et al (2006) and Melen et al (2012Melen et al ( , 2013]. These included the molecular structures and packing of a number of related 1,3diaza-2,4-dithiabuta-1,2-dienes.…”