biostudies-literatureSugimoto HNIGMS NIH HHS5368-70https://www.ebi.ac.uk/biostudies/studies/S-EPMC4020915biostudies-literatureUnknown49(12)A monooxomolybdenum(VI) model complex for the oxidized active site in the DMSOR family of molybdoenzymes has been synthesized and structurally characterized. The compound was obtained from the desoxomolybdenum(IV) derivative by clean oxygen-atom transfer from an amine N-oxide in a manner similar to that observed in the enzyme. A combination of electronic absorption and resonance Raman spectroscopies, coupled with the results of bonding and excited-state calculations, has been used to provide strong support for a highly covalent Mo(d(xy))-S(dithiolene) pi*-bonding interaction in the molybdenum(VI) complex. It is proposed that the resulting Mo-S covalency facilitates electron-transfer regeneration of the catalytically competent DMSOR Mo(IV) active site.Inorganic chemistryMonooxomolybdenum(VI) complexes possessing olefinic dithiolene ligands: probing Mo-S covalency contributions to electron transfer in dimethyl sulfoxide reductase family molybdoenzymes.PMC4020915R01 GM057378GM-057378Mtei RPSuyama KSugimoto HTatemoto SMiyake HItoh SKirk MLfalseMonooxomolybdenum(VI) complexes possessing olefinic dithiolene ligands: probing Mo-S covalency contributions to electron transfer in dimethyl sulfoxide reductase family molybdoenzymes.A monooxomolybdenum(VI) model complex for the oxidized active site in the DMSOR family of molybdoenzymes has been synthesized and structurally characterized. The compound was obtained from the desoxomolybdenum(IV) derivative by clean oxygen-atom transfer from an amine N-oxide in a manner similar to that observed in the enzyme. A combination of electronic absorption and resonance Raman spectroscopies, coupled with the results of bonding and excited-state calculations, has been used to provide strong support for a highly covalent Mo(d(xy))-S(dithiolene) pi*-bonding interaction in the molybdenum(VI) complex. It is proposed that the resulting Mo-S covalency facilitates electron-transfer regeneration of the catalytically competent DMSOR Mo(IV) active site.2010-01-01T00:00:00Z2010 Jun2020-10-31T09:22:15Z2019-03-27T01:28:11ZS-EPMC40209152049145410.1021/ic100825x