Interactions of organic molecules with low valent tungsten aryloxide compounds
Abstract
The recent development of a series of tungsten aryloxide complexes, [W(OC 6HPh3-η6-C6H5)(OC 6HPh4-2,3,5,6)(PR3)], has been shown to be capable of performing four electron reductions of O2, diazines, and nitroso compounds at a single metal center. These compounds were revealed to be highly reactive with a wide range of organic substrates, such as imines, chalcogens, ketones and aldehydes. Mechanistic studies of this system has been carried out in order to gain a greater understanding of this reaction, since only 3 systems are currently known that are capable of four electron reductions at a single metal center. Both the nature of the initial binding of the diazines to the metal center and the effects of the configuration of the diazine substrates upon the reaction were studied. Investigations found that increasing the rate of these reactions was possible in the case of the diazines by photolysis or heating the solution. Excess phosphine was found to inhibit the reaction. The solid state structures of [W(OC6HPh3-η 6-C6H5)(OC6HPh4-2,3,5,6)(PR 3)] {PR3 = PMe3, PEt3, PBun3, and PMe2Ph} were studied and the dynamics of these molecules in aromatic hydrocarbon solutions were also examined.
Degree
Ph.D.
Advisors
Rothwell, Purdue University.
Subject Area
Chemistry|Organic chemistry
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