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Cobalt‐Catalyzed Selective Oxidation of the Tritertiary Phosphane Triphos with Molecular Oxygen
Author(s) -
Heinze Katja,
Huttner Gottfried,
Zsolnai Laszlo
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971301007
Subject(s) - triphos , chemistry , catalysis , reactivity (psychology) , cobalt , medicinal chemistry , ligand (biochemistry) , yield (engineering) , oxygen , reaction mechanism , stereochemistry , organic chemistry , receptor , medicine , biochemistry , materials science , alternative medicine , pathology , metallurgy
The reactivity of complexes of triphos [CH 3 C(CH 2 PPh 2 ) 3 ] and CoCl 2 towards dioxygen has been investigated. Reaction of the pseudo‐tetrahedral complex (η 2 ‐triphos)CoCl 2 ( 1 ) with dioxygen yields after work‐up the mixed phosphane/phosphane oxide ligands triphosO and triphosO 2 . The novel ligand triphosO 2 can be obtained in quantitative yield using catalytic amounts of 1 . In order to gain some insight into the catalytic dioxygen activation reaction, experiments with various triphos/Co/Cl species, in different solvents and at several concentrations have been carried out. A mechanism involving two separate reaction pathways is proposed. Complexes of triphosO and triphosO 2 with CoCl 2 , [η 2 ‐( P, P )‐triphosO]CoCl 2 ( 4 ), and [η 2 ‐( P, O )‐triphosO 2 ]CoCl 2 ( 5 ), which are present as intermediates in the oxygenation reaction, have been isolated and fully characterized including X‐ray structural analyses.