Reactions of benzo[b]thiophene with some aqueous platinum metal species at elevated temperatures

• Published in: Canadian journal of chemistry Vol. 69; no. 4; pp. 590 - 598
• Main Authors: Clark, Peter D, Fait, James F, Jones, Colin G, Kirk, Martin J
• Format: Journal Article
• Language: English
• Published: Ottawa, Canada NRC Research Press 01.04.1991; National Research Council of Canada
• Subjects: Chemistry; Condensed matter: structure, mechanical and thermal properties; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Inorganic compounds; Metal complexes; Organic chemistry; Physics; Preparations and properties; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Desulfurization; Temperature; Molecular structure; Platinum Chlorides; Organic ligand; Palladium III Complexes; Transition metal Chlorides; Experimental study; X ray diffraction; Sulfur heterocycle; Aqueous medium; Trans stereoisomer; Bicyclic compound; Chloro complex; Aromatic compound; Platinoid Complexes; Crystalline structure
• ISSN: 0008-4042; 1480-3291
• DOI: 10.1139/v91-089

The desulfurization of benzo[b]thiophene 1 with aqueous transition metal species in the presence of various hydrocarbons at elevated temperatures is described. Mechanistic studies have shown that treatment of 1 with solutions of RuCl 3 and other platinum metal species results in the formation of 2,3-dihydrobenzo[b]thiophene 2 and ethylbenzene 3 as major products. Metal coordinated species are probable intermediates in the formation of 2 and hydrocarbon products. 2 readily coordinates to PdCl 2 to form square-planar trans-dichlorobis(2,3-dihydrobenzo[b]thiophene) palladium(II), which decomposes to ethylbenzene at 300 °C. The crystal structure of the complex was determined by a single crystal X-ray diffraction study. The complex crystallized in the monoclinic space group C 2/c with Z = 8 in a cell of dimensions a = 23.057 (3), b = 9.711 (1), c = 15.227 (2) Å and β = 99.74(1)°. The structure was solved by the Fourier method and was refined by full-matrix least-squares calculations to R = 0.042 for 2537 observed data with I > 2.5σ(I). Key words: benzo[b]thiophene, desulfurization, platinum metal species.