Issuing Body

Mississippi State University

Advisor

Henry, William P.

Committee Member

Wipf, David

Committee Member

Sygula, Andrzej

Committee Member

Emerson, Joseph P.

Committee Member

Zhang, Dongmao

Date of Degree

1-1-2013

Document Type

Dissertation - Open Access

Major

Chemistry

Degree Name

Doctor of Philosophy

College

College of Arts and Sciences

Department

Department of Chemistry

Abstract

The dissertation describes research work on development of bimetallic heterogeneous catalysts for oxidation of organic compounds. Binuclear metal complexes are an interesting class of compounds due to their catalytic activity. The approach involves anchoring a triketone ligand to Cab-O-Sil via a linker. Specifically, silica gel was allowed to react with p-chloromethylphenyltrimethoxysilane followed by coupling with deprotonated triketone compounds. The viability of this approach was verified by performing the benzylation reaction of triketones with benzyl halides under basic conditions. The benzylation of 2,4,6-heptanetrione and 1,5-diphenyl-1,3,5-pentanetrione is achieved with benzyl bromide using n-tetrabutylammonium fluoride as base. These benzylation reaction conditions were used to attach the triketones to the surface-attached linker. Once the ligand is attached to the silica gel, the catalyst is formed by coordinating two copper(II) ions from solution to the deprotonated triketone. The coordination of copper(II) ions to the triketone was monitored using UV-vis spectroscopy. The modified silica gel is characterized by diffuse reflectance infrared Fourier spectroscopy (DRIFTS), and thermal gravimetric analysis (TGA) at the different stages of catalyst formation. All techniques indicated significant attachment of linker and triketone to the support. The oxidation of 3,5-di-tert-butyl catechol (DTBC) and benzyl alcohol was carried out under aerobic conditions using these catalysts. The kinetics of the DTBC oxidation and benzyl alcohol oxidation was studied using bimetallic and monometallic catalytic systems. The copper complexes of the triketone ligands were also evaluated as catalysts for the oxidation of DTBC. New bimetallic metal complexes with triketone ligands having a benzyl group were synthesized and characterized by high resolution mass spectroscopy and IR spectroscopy. In addition to a detailed description of the synthesis and characterization of new triketone compounds, and the heterogeneous catalyst systems, a comparison of the kinetics of the oxidation of DTBC using these catalysts will be discussed.

URI

https://hdl.handle.net/11668/20353

Comments

benzylation||catechol||bimetallic

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