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Ethylene oxidation by a platinum(II) hydroxo complex. Insights into the wacker process

Citation

Weliange, NM and Sharp, PR, Ethylene oxidation by a platinum(II) hydroxo complex. Insights into the wacker process, Organometallics, 31, (19) pp. 6823-6833. ISSN 0276-7333 (2012) [Refereed Article]

Copyright Statement

Copyright 2012 American Chemical Society

DOI: doi:10.1021/om300626a

Abstract

The ethylene reaction of hydroxo complex [Pt(COD)(-OH)]2(OTf)2 (4) yields acetaldehyde and an equilibrium mixture of Pt(COD)(C2H5)(OTf) (6) and [Pt(COD)(C2H5)(2-C2H4)]OTf (7). Dinuclear [Pt2(COD)2(-OH){-2C,O-CH2C(O)H}](OTf)2 (10) and mononuclear Pt(COD)(CH2C(O)H)(OTf) (11) are detected as intermediates during the reaction. The reaction displays three phases: (1) an induction period, (2) an accelerating reaction yielding intermediate 11, water, and 6 plus 7, and (3) a linear decrease in the concentration of 11 with simultaneous formation of acetaldehyde and more 6 plus 7. The reaction is proton catalyzed, and phases 1 and 2 are attributed to autocatalytic behavior resulting from the acidic complex of 6 with water, [Pt(COD)(C2H5)(OH2)]OTf. Phase 3 is initiated by the complete consumption of basic 4 and the resulting release of protons to catalyze the reaction of 11 with water and ethylene to give acetaldehyde and 6 plus 7.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Transition Metal Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Weliange, NM (Dr Malathi Weliange)
ID Code:81037
Year Published:2012
Web of Science® Times Cited:7
Deposited By:Chemistry
Deposited On:2012-11-21
Last Modified:2013-05-08
Downloads:0

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