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A density functional study of oxygen atom transfer reactions between biological oxygen atom donors and molybdenum(IV) bis(dithiolene) complexes
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UNSPECIFIED. (2002) A density functional study of oxygen atom transfer reactions between biological oxygen atom donors and molybdenum(IV) bis(dithiolene) complexes. INORGANIC CHEMISTRY, 41 (25). pp. 6695-6702. ISSN 0020-1669
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Official URL: http://dx.doi.org/10.1021/ic020385h
Abstract
Density functional calculations have been used to investigate oxygen atom transfer reactions from the biological oxygen atom donors trimethylamine N-oxide (Me3NO) and dimethyl sulfoxide (DMSO) to the molybdenum(IV) complexes [MoO(mnt)(2)](2-) and [Mo(OCH3)(mnt)(2)](-) (mnt = maleonitrile-1,2-dithiolate), which may serve as models for mononuclear molybdenum enzymes of the DMSO reductase family. The reaction between [MoO(mnt)(2)](2-) and trimethylamine N-oxide was found to have an activation energy of 72 kJ/mol and proceed via a transition state (TS) with distorted octahedral geometry, where the MOO is bound through the oxygen to the molybdenum atom and the N-O bond is considerably weakened. The computational modeling of the reactions between dimethyl sulfoxide (DMSO) and [MoO(mnt)(2)](2-) or [Mo(OCH3)(mnt)(2)](-) indicated that the former is energetically unfavorable while the latter was found to be favorable. The addition of a methyl group to [MoO(mnt)(2)](2-) to form the corresponding des-oxo complex not only lowers the relative energy of the products but also lowers the activation energy. In addition, the reaction with [Mo(OCH3)(mnt)(2)](-) proceeds via a TS with trigonal prismatic geometry instead of the distorted octahedral TS geometry modeled for the reaction between [MoO(mnt)(2)](2-) and Me3NO.
| Item Type: | Journal Article |
|---|---|
| Subjects: | Q Science > QD Chemistry |
| Journal or Publication Title: | INORGANIC CHEMISTRY |
| Publisher: | AMER CHEMICAL SOC |
| ISSN: | 0020-1669 |
| Date: | 16 December 2002 |
| Volume: | 41 |
| Number: | 25 |
| Number of Pages: | 8 |
| Page Range: | pp. 6695-6702 |
| Identification Number: | 10.1021/ic020385h |
| Publication Status: | Published |
| URI: | http://wrap.warwick.ac.uk/id/eprint/10229 |
Data sourced from Thomson Reuters' Web of Knowledge
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