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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. doi:10.1021/ic020385h 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 | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Journal or Publication Title: | INORGANIC CHEMISTRY | ||||
Publisher: | AMER CHEMICAL SOC | ||||
ISSN: | 0020-1669 | ||||
Official Date: | 16 December 2002 | ||||
Dates: |
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Volume: | 41 | ||||
Number: | 25 | ||||
Number of Pages: | 8 | ||||
Page Range: | pp. 6695-6702 | ||||
DOI: | 10.1021/ic020385h | ||||
Publication Status: | Published |
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