Cobalt-Catalyzed Selective Oxidation of the Tritertiary Phosphane Triphos with Molecular Oxygen

✍ Scribed by Heinze, Katja ;Huttner, Gottfried ;Zsolnai, Laszlo

• Publisher: Wiley (John Wiley & Sons)
• Year: 1997
• Tongue: English
• Weight: 926 KB
• Volume: 130
• Category: Article
• ISSN: 0009-2940
• DOI: 10.1002/cber.19971301007

✦ Synopsis

The reactivity of complexes of triphos [CH3C(CH2PPh2J3] and CoC1, towards dioxygen has been investigated. Reaction of the pseudo-tetrahedral complex (q2-triphos)CoC12 (1) with dioxygen yields after work-up the mixed phosphane/phosphane oxide ligands triphosO and triphosO,. The novel ligand triphosO, 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 va-rious 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, with CoC12, [q2-(P,P)-tri-phosOjCoC1, (4), and [q2-(P,O)-tripho~O2]CoCl2 (5), which are present as intermediates in the oxygenation reaction, have been isolated and fully characterized including X-ray structural analyses.

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