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Synthesis and Reactivity Studies of Model Complexes for Molybdopterin-Dependent Enzymes

Thapper, Anders; Lorber, Christian; Fryxelius, Jacob; Behrens, Axel and Nordlander, Ebbe LU (2000) In Journal of Inorganic Biochemistry 79(1-4). p.67-74
Abstract
The molybdenum cofactor (Moco)-containing enzymes are divided into three classes that are named after prototypical members of each family, viz. sulfite oxidase, DMSO reductase and xanthine oxidase. Functional or structural models have been prepared for these three prototypical enzymes: (i) The complex [MoO2(mnt)2]2− (mnt2−=1,2-dicyanoethylenedithiolate) has been found to be able to oxidize hydrogen sulfite to HSO4− and is thus a functional model of sulfite oxidase. Kinetic and computational studies indicate that the reaction proceeds via attack of the substrate at one of the oxo ligands of the complex, rather than at the metal. (ii) The coordination geometries of the mono-oxo [Mo(VI)(O-Ser)(S2)2] entity (S2=dithiolene moiety of... (More)
The molybdenum cofactor (Moco)-containing enzymes are divided into three classes that are named after prototypical members of each family, viz. sulfite oxidase, DMSO reductase and xanthine oxidase. Functional or structural models have been prepared for these three prototypical enzymes: (i) The complex [MoO2(mnt)2]2− (mnt2−=1,2-dicyanoethylenedithiolate) has been found to be able to oxidize hydrogen sulfite to HSO4− and is thus a functional model of sulfite oxidase. Kinetic and computational studies indicate that the reaction proceeds via attack of the substrate at one of the oxo ligands of the complex, rather than at the metal. (ii) The coordination geometries of the mono-oxo [Mo(VI)(O-Ser)(S2)2] entity (S2=dithiolene moiety of molybdopterin) found in the crystal structure of R. sphaeroides DMSO reductase and the corresponding des-oxo Mo(IV) unit have been reproduced in the complexes [M(VI)O(OSiR3)(bdt)2] and [M(VI)O(OSiR3)(bdt)2] (M=Mo,W; bdt=benzene dithiolate). (iii) A facile route has been developed for the preparation of complexes containing a cis-Mo(VI)OS molybdenum oxo, sulfido moiety similar to that detected in the oxidized form of xanthine oxidase. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Oxotransferase, Molybdenum cofactor, Molybdopterin, Model complexes
in
Journal of Inorganic Biochemistry
volume
79
issue
1-4
pages
67 - 74
publisher
Elsevier
external identifiers
  • scopus:0034732617
ISSN
1873-3344
DOI
10.1016/S0162-0134(00)00010-6
language
English
LU publication?
yes
id
855008ef-9d8d-4c2a-919d-43cb722cd4c0 (old id 959665)
date added to LUP
2008-08-18 11:54:23
date last changed
2017-03-05 04:05:17
@article{855008ef-9d8d-4c2a-919d-43cb722cd4c0,
  abstract     = {The molybdenum cofactor (Moco)-containing enzymes are divided into three classes that are named after prototypical members of each family, viz. sulfite oxidase, DMSO reductase and xanthine oxidase. Functional or structural models have been prepared for these three prototypical enzymes: (i) The complex [MoO2(mnt)2]2− (mnt2−=1,2-dicyanoethylenedithiolate) has been found to be able to oxidize hydrogen sulfite to HSO4− and is thus a functional model of sulfite oxidase. Kinetic and computational studies indicate that the reaction proceeds via attack of the substrate at one of the oxo ligands of the complex, rather than at the metal. (ii) The coordination geometries of the mono-oxo [Mo(VI)(O-Ser)(S2)2] entity (S2=dithiolene moiety of molybdopterin) found in the crystal structure of R. sphaeroides DMSO reductase and the corresponding des-oxo Mo(IV) unit have been reproduced in the complexes [M(VI)O(OSiR3)(bdt)2] and [M(VI)O(OSiR3)(bdt)2] (M=Mo,W; bdt=benzene dithiolate). (iii) A facile route has been developed for the preparation of complexes containing a cis-Mo(VI)OS molybdenum oxo, sulfido moiety similar to that detected in the oxidized form of xanthine oxidase.},
  author       = {Thapper, Anders and Lorber, Christian and Fryxelius, Jacob and Behrens, Axel and Nordlander, Ebbe},
  issn         = {1873-3344},
  keyword      = {Oxotransferase,Molybdenum cofactor,Molybdopterin,Model complexes},
  language     = {eng},
  number       = {1-4},
  pages        = {67--74},
  publisher    = {Elsevier},
  series       = {Journal of Inorganic Biochemistry},
  title        = {Synthesis and Reactivity Studies of Model Complexes for Molybdopterin-Dependent Enzymes},
  url          = {http://dx.doi.org/10.1016/S0162-0134(00)00010-6},
  volume       = {79},
  year         = {2000},
}