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ACTIVATION AND FUNCTIONALIZATION OF C-H BONDS CATALYZED
BY OXYGEN AND NITROGEN LIGATED LATE TRANSITION METAL
COMPLEXES
by
Somesh Kumar Ganesh
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 Somesh Kumar Ganesh
Object Description
| Title | Activation and functionalization of C-H bonds catalyzed by oxygen and nitrogen ligated late transition metal complexes |
| Author | Ganesh, Somesh Kumar |
| Author email | skganesh@usc.edu; skganesh@gmail.com |
| Degree | Doctor of Philosophy |
| Document type | Dissertation |
| Degree program | Chemistry |
| School | College of Letters, Arts and Sciences |
| Date defended/completed | 2008-06-27 |
| Date submitted | 2008 |
| Restricted until | Unrestricted |
| Date published | 2008-09-12 |
| Advisor (committee chair) | Periana, Roy A. |
| Advisor (committee member) |
Prakash, Surya G.K. Petasis, Nicos A. Shing, Katherine |
| Abstract | This dissertation describes the usage of nitrogen and oxygenated ligand sets such as acetylacetone (acac), 6-phenyl-4,4’-bis(tert-butyl)-2,2’-bipyridine(NNC) on Iridium metal and diamine-bisphenolate (NNOO) on Rhodium for the activation of the C-H bonds of arenes and functionalization such as hydroarylation of olefins.; The first chapter is an introduction to CH activation and its importance towards CH bond functionalization. The use of acidic solvents for CH activation are also addressed and the catalyst inhibition by water or methanol. Approaches for the next generation of CH functionalization of catalysts are also addressed.; Chapter two addresses synthesis and characterization of air and thermally stables biamine-bisphenolate (NNOO)Rh(III)Cl(S) (X= Cl ,Ph; S = H2O , CH3OH) type complexes with the objective of designing new CH activation catalyst precursors having predisposed cis coordination states for CH activation. NMR and X-ray diffraction studies revealed that the NNOO ligands coordinate to Rh as nonplanar tetradentate ligands, with O,O donors either in a cis or trans position, depending on fairly subtle differences. DFT studies suggest that the preference for cis/trans-O,O is controlled by the bulk of the phenolate substituents, and the rigidity of the N-C-C-N bridge. Finally, transmetalation of the Rh-Cl bond with Ph2Hg led to a Rh-Phenyl complex with conserved geometry.; Our group has been exploring the chemistry of electron rich, tridentate pincer, NNC ligated, Ir(III) homogeneous complexes in order to identify systems that could be sufficiently thermally, protic and oxidant stable to allow coupling of the CH activation and M-R Functionalization reactions to generate functionalized products in new catalytic systems. We had earlier demonstrated that Ir(NNC)(C2H5)(TFA)(L) complexes where NNC is 6-phenyl-4,4'-(di-tert-butyl)-2,2'-bipyridine and L is NCCH3 or ethylene(C2H4) undergo stochiometric C-H activation of hydrocarbons at 110 oC. In chapter 3 we examine the mechanism for the catalytic H/D exchange between benzene and toluene with this system where R = Ph.; Chapter 4 summarizes the usage of air and water stable O-donor ligated, late metal complexes, (acac-O,O)2Ir(R)(L), based on the simplest β-diketonate, acetylacetonate for the anti-Markovnikov, hydroarylation of unactivated olefins, which has been shown to operate by arene C-H activation followed by olefin insertion. |
| Keyword | activation; functionalization; C-H bonds; transition metal complexes |
| 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-m1597 |
| Rights | Ganesh, Somesh Kumar |
| Repository name | Libraries, University of Southern California |
| Repository address | Los Angeles, California |
| Repository email | http://www.usc.edu/isd/libraries/services/ask_a_librarian/email/ |
| Filename | etd-Ganesh-2300 |
| Archival file | uscthesesreloadpub_Volume23/etd-Ganesh-2300.pdf |
Description
| Title | Page 1 |
| Full text | ACTIVATION AND FUNCTIONALIZATION OF C-H BONDS CATALYZED BY OXYGEN AND NITROGEN LIGATED LATE TRANSITION METAL COMPLEXES by Somesh Kumar Ganesh 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 Somesh Kumar Ganesh |
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