The difference one ligand atom makes - An altered oxygen transfer reaction mechanism caused by an exchange of selenium for sulfur

Carlos Enrique Abad Andrade; Xiaoli Ma; Wolfram Meyer-Klaucke; Carola Schulzke

doi:10.1016/j.poly.2009.10.018

The difference one ligand atom makes - An altered oxygen transfer reaction mechanism caused by an exchange of selenium for sulfur

Carlos Enrique Abad Andrade
, Xiaoli Ma
, Wolfram Meyer-Klaucke
, Carola Schulzke^*

^*Corresponding author for this work

University of Göttingen
Beijing Institute of Technology
European Molecular Biology Laboratory
Trinity College Dublin

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

Abstract

The influence of sulfur versus selenium coordination to molybdenum on the oxo transfer reaction mechanisms of functional models for oxidoreductases has been studied. The solution structure of the dimeric molybdenum compound with tridentate bis-anionic ligands containing a thioether function (^-O(CH₂)₃S(CH₂)₃O ^-) has been determined using EXAFS spectroscopy to be able to compare a feature of its solution structure to that of its selenoether analogue. A significant difference is found for the solution structures of the two compounds. The thioether group remains coordinated in solution, whereas the selenoether does not. The influence of this difference on the catalytic oxo transfer has been investigated in detail by following the catalytic transition of PPh₃ to OPPh₃ with DMSO as oxygen donor with variation of both substrate concentrations.

Original language	English
Pages (from-to)	664-668
Number of pages	5
Journal	Polyhedron
Volume	29
Issue number	1
DOIs	https://doi.org/10.1016/j.poly.2009.10.018
Publication status	Published - 13 Jan 2010
Externally published	Yes

Keywords

Catalysis
EXAFS spectroscopy
Ligand effects
Metalloenzymes
Molybdenum

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10.1016/j.poly.2009.10.018

Cite this

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title = "The difference one ligand atom makes - An altered oxygen transfer reaction mechanism caused by an exchange of selenium for sulfur",

abstract = "The influence of sulfur versus selenium coordination to molybdenum on the oxo transfer reaction mechanisms of functional models for oxidoreductases has been studied. The solution structure of the dimeric molybdenum compound with tridentate bis-anionic ligands containing a thioether function (-O(CH2)3S(CH2)3O -) has been determined using EXAFS spectroscopy to be able to compare a feature of its solution structure to that of its selenoether analogue. A significant difference is found for the solution structures of the two compounds. The thioether group remains coordinated in solution, whereas the selenoether does not. The influence of this difference on the catalytic oxo transfer has been investigated in detail by following the catalytic transition of PPh3 to OPPh3 with DMSO as oxygen donor with variation of both substrate concentrations.",

keywords = "Catalysis, EXAFS spectroscopy, Ligand effects, Metalloenzymes, Molybdenum",

author = "\{Abad Andrade\}, \{Carlos Enrique\} and Xiaoli Ma and Wolfram Meyer-Klaucke and Carola Schulzke",

year = "2010",

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doi = "10.1016/j.poly.2009.10.018",

language = "English",

volume = "29",

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journal = "Polyhedron",

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TY - JOUR

T1 - The difference one ligand atom makes - An altered oxygen transfer reaction mechanism caused by an exchange of selenium for sulfur

AU - Abad Andrade, Carlos Enrique

AU - Ma, Xiaoli

AU - Meyer-Klaucke, Wolfram

AU - Schulzke, Carola

PY - 2010/1/13

Y1 - 2010/1/13

N2 - The influence of sulfur versus selenium coordination to molybdenum on the oxo transfer reaction mechanisms of functional models for oxidoreductases has been studied. The solution structure of the dimeric molybdenum compound with tridentate bis-anionic ligands containing a thioether function (-O(CH2)3S(CH2)3O -) has been determined using EXAFS spectroscopy to be able to compare a feature of its solution structure to that of its selenoether analogue. A significant difference is found for the solution structures of the two compounds. The thioether group remains coordinated in solution, whereas the selenoether does not. The influence of this difference on the catalytic oxo transfer has been investigated in detail by following the catalytic transition of PPh3 to OPPh3 with DMSO as oxygen donor with variation of both substrate concentrations.

AB - The influence of sulfur versus selenium coordination to molybdenum on the oxo transfer reaction mechanisms of functional models for oxidoreductases has been studied. The solution structure of the dimeric molybdenum compound with tridentate bis-anionic ligands containing a thioether function (-O(CH2)3S(CH2)3O -) has been determined using EXAFS spectroscopy to be able to compare a feature of its solution structure to that of its selenoether analogue. A significant difference is found for the solution structures of the two compounds. The thioether group remains coordinated in solution, whereas the selenoether does not. The influence of this difference on the catalytic oxo transfer has been investigated in detail by following the catalytic transition of PPh3 to OPPh3 with DMSO as oxygen donor with variation of both substrate concentrations.

KW - Catalysis

KW - EXAFS spectroscopy

KW - Ligand effects

KW - Metalloenzymes

KW - Molybdenum

UR - https://www.scopus.com/pages/publications/79551678144

U2 - 10.1016/j.poly.2009.10.018

DO - 10.1016/j.poly.2009.10.018

M3 - Article

AN - SCOPUS:79551678144

SN - 0277-5387

VL - 29

SP - 664

EP - 668

JO - Polyhedron

JF - Polyhedron

IS - 1

ER -

The difference one ligand atom makes - An altered oxygen transfer reaction mechanism caused by an exchange of selenium for sulfur

Abstract

Keywords

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