56391-52-7Relevant academic research and scientific papers
Synthesis of a stable disulfur monoxide precursor and trapping of disulfur monoxide with transition-metal complexes
Urove, Greg A.,Welker, Mark E.
, p. 1013 - 1014 (1988)
A five-step synthesis of 4,5-diphenyl-3,6-dihydro-1,2-dithiin 1-oxide starting from 2,3-diphenylmaleic anhydride is described. When the dithiin 1-oxide was treated with coordinatively unsaturated transition-metal complexes, a transition-metal disulfur monoxide complex and 2,3-diphenylbutadiene were isolated.
Investigation of a transition metal-assisted retro Diels-Alder reaction used in the synthesis of transition metal S2O complexes
Urove, Greg A.,Welker, Mark E.,Eaton, Bruce E.
, p. 105 - 114 (2007/10/02)
Treatment of 4,5-diphenyl-3,6-dihydro-1,2-dithiin-1-oxide with coordinatively unsaturated transition metal complexes resulted in the production of S2O complexes and 2,3-diphenylbutadiene.A transition metal-assisted retro Diels-Alder mechanism has been proposed for this reaction.A series of IR and 1H NMR experiments and MNDO calculations on 4,5-diphenyl-3,6-dihydro-1,2-dithiin-1-oxide have been performed to gain additional information about this transformation.
Peracid oxidation of inorganic chalcogen ligands in transition metal complexes
Hoots, John E.,Lesch, David A.,Rauchfuss, Thomas B.
, p. 3130 - 3136 (2008/10/08)
The use of organic peracids as rapid, selective oxidation agents for coordinated chalcogens, η2-E2 (E = S, Se) and μ3-E (E = S, Se, Te), has been examined. Stepwise oxidation of [Ir(η2-S2)(dppe)2]PF6 with m-chloroperbenzoic acid (m-CPBA) yielded [Ir(η2-S2O)(dppe)2]PF6 (1) and [Ir(η2-S2O2)(dppe)2]PF 6 (2). Facile oxidation of [Ir(η2-Se2)(dppe)2]PF6 and Cp2Nb(η2-S2)Cl with peracetic acid produced [Ir(η2-Se2O)(dppe)2]PF6 (3) and Cp2Nb(η2-S2O)Cl (4). Similarly, reaction of Fe3(μ3-S)2(CO)9 and Fe2Pt(μ3-E)2(CO)6(PPh 3)2 (E = S, Se, Te) with m-CPBA produced the chalcogen monoxide complexes, Fe3(μ3-SO)(μ3-S)(CO)9 (5) and Fe2Pt(μ3-EO)(μ3-E)(CO) 6(PPh3)2 (6). The stereochemistry and reactivity of all of these complexes have been studied. Reaction of the η2-S2O complexes with nucleophiles (Nu = PPh3, CH3NC) revealed sulfur transfer as the favored reaction and the unsubstituted sulfur donor atom as the most reactive site. Attempted formation of η1- or η2-SO complexes by selective sulfur-abstraction reactions was unsuccessful, but an unsymmetrical dichalcogenide complex, [Ir(η2-SSe)(dppe)2]+ (7), was synthesized from [Ir(dppe)2]Cl and Cp2TiSxSe5-x (x ≈ 3). Examination of the oxygen-transfer capabilities of the iridium complexes revealed the following trend: Se2O ? S2O2 > S2O. In solution, the [Ir(Se2O)(dppe)2]PF6 complex spontaneously eliminates the exocyclic oxygen to yield [Ir(Se2)(dppe)2]+ and oxidizes C2H5SH to ethyl disulfide. In contrast, the [Ir(S2O)(dppe)2]Cl and Cp2Nb(S2O)Cl complexes show a pronounced tendency toward sulfur transfer to substrates but virtually no oxygen-transfer capability. The μ3-SO complexes proved to be virtually inert toward both O- and S-transfer reactions. Also described is the utility of chiral solvating and lanthanide shift reagents in the elucidation of the structure and stereochemistry of Cp2Nb(S2O)Cl using 1H NMR spectroscopy.
