Mechanistic investigation of trimethylamine-N-oxide reduction catalysed by biomimetic molybdenum enzyme modelsElectronic supplementary information (ESI) available. See DOI: 10.1039/c5cp07278f
In this paper, we report a theoretical investigation of the reduction reaction mechanism of Me 3 NO using molybdenum containing systems that are functional and structural analogues of trimethylamine N -oxide reductase mononuclear molybdenum enzyme. The reactivity of the monooxomolybdenum( iv ) benze...
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Main Authors | , , , |
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Format | Journal Article |
Published |
16.03.2016
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Online Access | Get full text |
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Summary: | In this paper, we report a theoretical investigation of the reduction reaction mechanism of Me
3
NO using molybdenum containing systems that are functional and structural analogues of trimethylamine
N
-oxide reductase mononuclear molybdenum enzyme. The reactivity of the monooxomolybdenum(
iv
) benzenedithiolato complex and its derivatives to carbamoyl (
t
-BuNHCO) and acylamino (
t
-BuCONH) substituents on the benzene rings in both
cis
and
trans
arrangements was explored. The calculated energy profiles describing the steps of two mechanisms of attack considered viable (named
cis
- and
trans
-attack) by the Me
3
NO substrate at
cis
and
trans
positions with respect to the oxo ligand show that the attack on
cis
is energetically more favourable than the attack on
trans
. Along the pathway for the
cis
-attack the first step of the reaction, that is rate-determining for all the studied compounds, is the approach of the substrate to the Mo centre in
cis
to the oxo ligand that causes a distortion of the initial square-pyramidal geometry of the complex. The reaction steps involved in the
trans
position attack were also explored. Calculations confirm that, as previously suggested, the introduction of ligands able to form intramolecular NH S hydrogen bonds accelerates the reduction of the Me
3
NO substrate and contributes to the tuning of the reactivity of molybdoenzyme models.
In this paper, we report a theoretical investigation of the reduction reaction mechanism of Me
3
NO using molybdenum containing systems that are functional and structural analogues of trimethylamine
N
-oxide reductase mononuclear molybdenum enzyme. |
---|---|
Bibliography: | 10.1039/c5cp07278f Electronic supplementary information (ESI) available. See DOI |
ISSN: | 1463-9076 1463-9084 |
DOI: | 10.1039/c5cp07278f |