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Structural, Electrochemical, and Theoretical Investigations of New Thio‐ and Selenoether Complexes of Molybdenum and Tungsten
Author(s) -
Ma Xiaoli,
Starke Kerstin,
Schulzke Carola,
Schmidt HansGeorg,
Noltemeyer Mathias
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200500698
Subject(s) - molybdenum , chemistry , tungsten , trimer , dimer , electrochemistry , crystal structure , tungsten compounds , crystallography , ligand (biochemistry) , inorganic chemistry , organic chemistry , electrode , biochemistry , receptor
Molybdenum and tungsten complexes with tridentate bisanionic ligands ( – OC 2 H 4 XC 2 H 4 O – , X = S, Se) were synthesized and analyzed electrochemically. Crystal structures of [{MoO 2 [O(CH 2 ) 2 S(CH 2 ) 2 O]} 2 ] and [{WO 2 [O(CH 2 ) 2 S(CH 2 ) 2 O]} 3 ] were obtained. For these two complexes as well asfor the virtual molybdenum trimer and the tungsten dimer,DFT calculations were performed in order to better understand the formation of two significantly different complexes for molybdenum and tungsten with the same ligandand by the same preparation method. The compound WO 2 Cl 2 [MeS(CH 2 ) 2 SMe] was synthesized and characterized by crystal structure analysis. A structural and electrochemical comparison of this compound with the recently published analogous molybdenum compound and the dme analogs of molybdenum and tungsten were undertaken. All these data were used to evaluate the structural and electronic influences of replacing molybdenum by tungsten and of varying the ligand atoms (O/S/Se) from the point of view of the different coordination spheres of the molybdopterin‐dependent oxygen‐atom‐transfer enzymes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)