253310-20-2Relevant academic research and scientific papers
Stoichiometric O2 oxidation of bis(Thioether)(Octaethylporphyrinato)ruthenium(II) complexes to the corresponding sulfoxide species in acidic media. Structural confirmation of S-bonded sulfoxides
Pacheco, Andrew,James, Brian R.,Rettig, Steven J.
, p. 5579 - 5587 (2008/10/08)
Exposure to O2 (or air) of a CH2Cl2, benzene, or toluene solution containing PhCO2H and Ru(OEP)(RR′S)2 (where OEP = the dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin, R = methyl, ethyl, or decyl, and R′ = methyl or ethyl), at ambient conditions, results in the selective oxidation of the axial ligand(s) on the metalloporphyrin complex to the corresponding sulfoxide(s). For example, a CD2Cl2 solution of Ru(OEP)(dms)2 (dms = dimethyl sulfide) and PhCO2H, exposed to 1 atm of O2 at ～20 °C for 35 h, is oxidized to Ru(OEP)(dmso)2, and the intermediates Ru(OEP)(dms)(dmso), [Ru(OEP)(dms)2][PhCO2], and Ru(OEP)(dms)(PhCO2) are identified (s implies sulfur-bonded). Mechanisms invoking in situ formation of H2O2, disproportionation of Ruln species, and RuIV=O intermediates are proposed for the O2 oxidation of the thioether ligands. X-ray analysis of Ru(OEP)(Et2SO)2 confirms that the sulfoxides are S-bonded.
