Vanadium Thiolate Complexes for Efficient and Selective Sulfoxidation Catalysis: A Mechanistic Investigation.

{The structural and electronic properties as well as the catalytic activity toward sulfoxidn. of two new vanadium complexes have been investigated. They both possess in their coordination sphere two alkyl thiolate ligands: a dioxido VV complex VO2LNS2-HNEt3 (1) LNS2 = 2,2'-pyridine-2,6-diyl-bis-1,1'-diphenylethanethiol and an oxido VIV complex VOLN2S2 (2) LN2S2 = 2,2'-2,2'-bipyridine-6,6'-diyl-bis-1,1'-diphenylethanethiol. The X-ray structure of 1 has revealed that the VV metal ion is at the center of a distorted trigonal bipyramid. The optimized structure of 2 obtained by DFT calcns. displays a square-pyramidal geometry, consistent with its EPR spectrum characterized by an axial S = 1/2 signal g⊥ = 1.988, g‖ = 1.966, Ax(V) = 45 × 10-4 cm-1

Références

Titre
Vanadium Thiolate Complexes for Efficient and Selective Sulfoxidation Catalysis: A Mechanistic Investigation.
Type de publication
Article de revue
Année de publication
2013
Revue
Inorg. Chem.
Volume
52
Pagination
13424–13431
ISSN
0020-1669
Soumis le 12 avril 2018