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TOWARD A CATALYTIC SYSTEM FOR THE HYDROXYLATION OF METHANE:
OXY-FUNCTIONALIZATION OF ELECTRON RICH M-CH3 BONDS
by
Brian Lee Conley
A Dissertation Presented to the
FACULTY OF THE GRADUATE SCHOOL
UNIVERSITY OF SOUTHERN CALIFORNIA
In Partial Fulfillment of the
Requirements for the Degree
DOCTOR OF PHILOSOPHY
(CHEMISTRY)
December 2008
Copyright 2008 Brian Lee Conley
Object Description
| Title | Toward a catalytic cycle for the hydroxylation of methane: oxy-functionalization of electron rich M-CH3 bonds |
| Author | Conley, Brian Lee |
| Author email | brianlconley@gmail.com; bconley@usc.edu |
| Degree | Doctor of Philosophy |
| Document type | Dissertation |
| Degree program | Chemistry |
| School | College of Letters, Arts and Sciences |
| Date defended/completed | 2008-07-08 |
| Date submitted | 2008 |
| Restricted until | Unrestricted |
| Date published | 2008-12-04 |
| Advisor (committee chair) | Periana, Roy A. |
| Advisor (committee member) |
Prakash, Surya Williams, Travis J. Petruska, John A. |
| Abstract | The chemistry discussed herein involves the strategy of selective oxy-functionalization of well defined, electron-rich (and nucleophilic), M-CH3 bonds by O-atom insertion or methyl transfer reaction and a homogeneous system that exhibits C-H activation of a variety of bonds. These projects were undertaken with the goal of adding conceptual and practical knowledge to the development of a catalytic cycle for the conversion of hydrocarbons (particularly methane) to alcohols (methanol).; Chapter one introduces the strategy of C-H activation of methane as it pertains to using natural gas as a feedstock. It discusses the utility of employing selective reactions at C-H bonds, some pitfalls of current systems, and the strategy of incorporating an oxy-functionalization reaction for more nucleophilic metals.; Chapter two describes oxy-functionalization of a model transition metal-methyl species, methyltrioxorhenium (MTO) by a variety of O-atom donors to produce methanol including theoretical work used to supplement and validate the experimental findings.; Chapter three is a research that elucidates a new (3+2) mechanism for oxy-functionalization of M-C bonds using cis-dioxo oxidants like OsO4 and describes the required base activation of the M-CH3 species.; Chapter four conveys a new strategy for functionalization of low-valent M-CH3 bonds by transfer of the methyl to a co-catalyst and subsequent oxidation/reduction steps to produce methanol.; Chapter five is research directed at finding new catalyst for hydroarylation of olefins, highlighting a novel Rh system that affords stoichiometric reactions with C-H bonds. |
| Keyword | methane; oxygen; oxy-functionalization; insertion; O-atom donor |
| Language | English |
| Part of collection | University of Southern California dissertations and theses |
| Publisher (of the original version) | University of Southern California |
| Place of publication (of the original version) | Los Angeles, California |
| Publisher (of the digital version) | University of Southern California. Libraries |
| Provenance | Electronically uploaded by the author |
| Type | texts |
| Legacy record ID | usctheses-m1870 |
| Contributing entity | University of Southern California |
| Rights | Conley, Brian Lee |
| Repository name | Libraries, University of Southern California |
| Repository address | Los Angeles, California |
| Repository email | cisadmin@dots.usc.edu |
| Filename | etd-Conley-2502 |
| Archival file | uscthesesreloadpub_Volume40/etd-Conley-2502.pdf |
Description
| Title | Page 1 |
| Contributing entity | University of Southern California |
| Repository email | cisadmin@dots.usc.edu |
| Full text | TOWARD A CATALYTIC SYSTEM FOR THE HYDROXYLATION OF METHANE: OXY-FUNCTIONALIZATION OF ELECTRON RICH M-CH3 BONDS by Brian Lee Conley A Dissertation Presented to the FACULTY OF THE GRADUATE SCHOOL UNIVERSITY OF SOUTHERN CALIFORNIA In Partial Fulfillment of the Requirements for the Degree DOCTOR OF PHILOSOPHY (CHEMISTRY) December 2008 Copyright 2008 Brian Lee Conley |
