Desulfurization of organosulfur compounds is highly important due to its relevance to the hydrodesulfurization process of fossil fuels, which removes sulfur from crude oil as H2S. Complete removal of sulfur from dibenzothiophene using low-valent Mo/W complexes at high temperatures has been reported previously. A reaction system involving Co(BF4)2·6H2O and a dinucleating ligand HPhBIMP, has been developed, which could desulfurize a large number of thiophenes, sulfides, thiols and disulfides at RT to generate the complex, [Co2(PhBIMP)(μ2-SH)(DMF)]2+, while the substrates are mostly converted to the corresponding alcohols/phenols. While a similar reaction system involving Fe(BF4)2.6H2O could also disulfurize thiols and disulfides quite efficiently to generate [Fe2(PhBIMP)(μ2-SH)(DMF)]2+, the reaction could not be extended to include thiophenes and sulfides. In case of both the Co(II) and Fe(II) mediated desulfurization reactions the plausible reaction intermediate [M2(PhBIMP)(H2O)2(DMF)2]3+(M=Co, Fe) have been isolated and characterized by single crystal X-Ray structure determination. During the Fe(II)-mediated desulfurization of disulfides a key reaction intermediate, [Fe2(PhBIMP)(MeCOSS)]2+ has been isolated, which was generated after the cleavage of only one C-S bond in MeC(O)S-SC(O)Me and thus, indicated that the C-S bond cleavage step may precede the S-S bond cleavage step.

Co(II)- and Fe(II)-Mediated Desulfurization of Organosulfur Substrates

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