Syntheses and Characterization of the MF₆^-(M = As, Sb) Salts of the Simple Trithietanylium PhCS₃⁺Cation and the Identity of PhCS₃Cl

Abstract

MF6- (M = As or Sb) salts of a simple derivative of the trithietanylium PhCSSS+, 1, were synthesized for the first time by the reaction of PhCS3Cl and AgMF6 in liquid SO2. 1SbF6 was characterized by IR, FT-Raman, and NMR spectroscopy, elemental analysis, and a preliminary X-ray crystal structure. 1AsF6 was characterized by 1H NMR and FT-Raman spectroscopy. The calculated (MPW1PW91/3-21G* or 6-31G*) geometries, 1H and 13C chemical shifts (MPW1PW91/6-311G(2DF)//MPW1PW91/3-21G*), and vibrational frequencies and intensities (MPW1PW91/6-31G*) were in satisfactory agreement with the observed values. The calculated pi type molecular orbitals of HCSSS+ (MPW1PW91/6-311+G*) and 1 (MPW1PW91/3-21G*) imply that the 6pi-CSSS+ ring has some aromatic character. 1SbF6 undergoes a metathesis reaction with NBu4Cl in liquid SO2 to give PhCS3Cl, which was characterized by vibrational spectroscopy and mass spectrometry. The evidence indicates that PhCS3Cl has the ionic formulation PhCSSS+ Cl- with significant cation-anion interactions in the solid state. ArCSSS+ SbF6- (Ar = 1-naphthyl), 14SbF6, was prepared from ArCS3Cl and AgSbF6, suggesting that the synthesis of MF6- (M = As or Sb) salts of RCSSS+ is potentially general for aryl derivatives. The structure of 14SbF6 was established by 1H and 13C NMR, IR, and FT-Raman spectroscopy, and theoretical calculations gave values in agreement with the experimental data.

Synthesis and characterization of copper sulfide nanocrystallites with low sintering temperatures

“…1020 cm À1 to the C]S stretch. 29,30 In fact, there exists much similarity in the IR spectra of the nanoparticles compared to that of benzylthiol, 31 with the notable exception of an absorption typical of the thiol groups (S-H) at 2565 cm À1 , only seen in the case of benzylthiol.…”

RCNSSS+: A novel class of stable sulfur rich radical cations

“…In the case of MeCN, despite its sufficiently high I.P. of 12.2 eV, a complex reaction gave the products 25a-25d, among which 25a is the first example of CSSS + heterocycle (Scheme 5) [135,138].…”

Oxygen, sulfur, selenium and tellurium

“…45 The reaction of PhCS 3 Cl and Ag[MF 6 ] (M ¼ As or Sb) gives trithietanylium salts [PhCS 3 ][MF 6 ], the 6p-CSSS 1 ring being calculated to possess some aromatic character. 46 Reports on phosphorus-chalcogencompounds include a new route for the bulk-scale preparation of the selenating agent [PhP(Se)(m-Se)] 2 (Woollins' Reagent), 47 ammonium salts of pyridine-stabilised monometatrithiophosphate [py-PS 3 ] À , 48 and the synthesis and reactivity of O-acylselenophosphates 49 and enantiomerically pure P-chiral phosphinoselenoic chlorides. 50 We focus now on the co-ordination chemistry of chalcogen donor ligands, beginning with phosphorus chalcogenides.…”