Synthesis and Properties of Ph₂S(N(Ph₂)S⋮N)₂

Abstract

A new type of lambda6-sulfanenitrile with an SN triple bond at both ends, Ph2S(=N-(Ph2)S[triple bond]N)2 (5), was prepared in excellent yield from the one-pot synthesis of diphenylsulfimide (Ph2SNH) with fluoro(diphenyl)-lambda6-sulfanenitrile (Ph2FSN) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene. Its molecular structure was determined by X-ray crystallographic analysis. Compound 5 reacted further with methyl triflate and trifluoromethanesulfonic anhydride to afford the corresponding bis-N-methylated and -N-sulfonated compounds.

Syntheses and Crystal Structures of and

“…Mews et al prepared trifluoro-λ 6 -sulfanenitrile (F 3 S≡N) and its derivatives (F 2 RS≡N, e.g., R = Me 2 N-, F 2 (O=)S=N-), and investigated their metal coordination chemistry [1][2][3]. Recently, we prepared fluoro(diphenyl)-λ 6 -sulfanenitrile (Ph 2 FS≡N) and reported the formation of the various substituted λ 6 -sulfanenitriles [4][5][6][7][8][9][10][11][12][13][14]. Among them, new types of λ 6 -sulfanenitrile with nitrilo and imino groups (type A) or two nitrilo groups (ndsdsd, type B) at both ends have been shown to complexes as bidentate N,N' ligands.…”

Oxygen, sulfur, selenium and tellurium

“…15 The reaction between Ph 2 SNH and Ph 2 FSRN in the presence of dbu produces Ph 2 S(QN-Ph 2 SRN) 2 , which has two terminal SRN bonds. 16 Chalcogenadiazoles and dichalcogenadiazoles (C 2 EN 2 and CE 2 N 2 rings, respectively), when fused to aromatic ring systems, exhibit useful conducting and optical properties; [17][18][19][20][21][22][23][24][25][26][27][28][29][30] prominent results include the synthesis of a biradical containing 1,2,3,5-and 1,3,2,4-isomeric dithiadiazolyl rings, 23 the polymorphism of the sterically crowded radical 2,4,6-(CF 3 ) 3 C 6 H 2 CNSSN d , 21 and the first monomeric pstacked bis-1,2,3-thiaselenazolyl radical. 19 Moving onto chalcogen-halogen species, the phenylselenium(IV) trihalides PhSeX 3 (X ¼ Cl or Br), derived by halogenation of Ph 2 Se 2 with SO 2 Cl 2 or Br 2 , exhibit very different structures.…”