Density functional study on the mechanism of the vanadium-catalyzed oxidation of sulfides by hydrogen peroxide

被引:49
作者
Balcells, D [1 ]
Maseras, F [1 ]
Lledós, A [1 ]
机构
[1] Univ Autonoma Barcelona, Unitat Quim Fis, Bellaterra 08193, Catalonia, Spain
关键词
D O I
10.1021/jo034052t
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A computational study with the Becke3LYP method is carried out on the mechanism of the reaction of complexes V(O)(L)(OOH) and V(O)(LH)(OO) (L = O(CH)(3)N(CH2)(2)O) with CH3S-SCH3, a system that stands as a model for experimental systems where the metal complex contains larger chelating Schiff bases and the substrate is bis(tert-butyl) disulfide. The different possible isomers of both the hydroperoxo V(O)(L)(OOH) and the peroxo V(O)(LH)(OO) forms of the catalyst are explored, and the reactivity of the most stable among them with the dimethyl disulfide substrate is studied through location of the corresponding transition states. A large variety of reactive paths happen to exist, though in all cases the reaction takes place through a direct transfer process, with the simultaneous formation of the S-O bond and breaking of the O-O bond being the rate-limiting step.
引用
收藏
页码:4265 / 4274
页数:10
相关论文
共 80 条
[1]   Catalytic oxidations by peroxy, peroxo and oxo metal complexes:: an interdisciplinary account with a personal view [J].
Adam, W ;
Malisch, W ;
Roschmann, KJ ;
Saha-Möller, CR ;
Schenk, WA .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2002, 661 (1-2) :3-16
[2]   Titanium-catalyzed, asymmetric sulfoxidation of alkyl aryl sulfides with optically active hydroperoxides [J].
Adam, W ;
Korb, MN ;
Roschmann, KJ ;
Saha-Möller, CR .
JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (10) :3423-3428
[3]   Activation of bis(trimethylsilyl) peroxide and tert-butyl hydroperoxide with oxo and peroxo complexes of vanadium, molybdenum, and tungsten for the sulfoxidation of thianthrene 5-oxide [J].
Adam, W ;
Golsch, D ;
Sundermeyer, J ;
Wahl, G .
CHEMISCHE BERICHTE, 1996, 129 (10) :1177-1182
[4]   OPTICALLY ACTIVE SULFOXIDES . SYNTHESIS + ROTATORY DISPERSION OF SOME DIARYL SULFOXIDES [J].
ANDERSEN, KK ;
FOLEY, JW ;
GAFFIELD, W ;
PAPANIKOLAU, NE ;
PERKINS, RI .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1964, 86 (24) :5637-+
[5]  
Baboul AG, 1998, J COMPUT CHEM, V19, P1353, DOI 10.1002/(SICI)1096-987X(199809)19:12<1353::AID-JCC4>3.0.CO
[6]  
2-H
[7]   ON THE MECHANISM OF METAL-CATALYZED EPOXIDATION - A MODEL FOR THE BONDING IN PEROXO METAL-COMPLEXES [J].
BACH, RD ;
WOLBER, GJ ;
CODDENS, BA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (20) :6098-6099
[8]   Selective and mild oxidation of sulfides to sulfoxides by oxodiperoxo molybdenum complexes adsorbed onto silica gel [J].
Batigalhia, F ;
Zaldini-Hernandes, M ;
Ferreira, AG ;
Malvestiti, I ;
Cass, QB .
TETRAHEDRON, 2001, 57 (48) :9669-9676
[9]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[10]   Enantioselective oxidation of di-tert-butyl disulfide with a vanadium catalyst:: Progress toward mechanism elucidation [J].
Blum, SA ;
Bergman, RG ;
Ellman, JA .
JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (01) :150-155