Journal
INORGANIC CHEMISTRY
Volume 49, Issue 12, Pages 5368-5370Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic100825x
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Funding
- NIGMS NIH HHS [R01 GM057378, GM-057378] Funding Source: Medline
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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(dxy) S(dithiolene) ye-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.
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