Synthesis and Reactivity of Transition Metal Complexes Supported by a Neutral Tetraamine Ligand Containing N,N'-dimethylaniline Units Público

Abstract

Abstract
Synthesis and Reactivity of Transition Metal Complexes Supported by a Neutral Tetraamine
Ligand Containing N,N'-dimethylaniline Units
By Lei Chu

A novel ligand tris(2-dimethylaminoaryl)amine, LMe, has been shown to coordinate with
some first row transition metals to produce firve-coordinate complexes with distorted trigonal
bipyramidal coordination geometry. For [Co(LMe)Br]BPh4, [Ni(LMe)Cl]BPh4, [Fe(LMe)Cl]BPh4
and [Cu(LMe)Cl]BF4, comparisons have been made to structures of related neutral ligand
tris(2-dimethylaminoethyl)amine, Me6tren. The results suggest that the more distorted
geometries of [M(LMe)X]+ complexes are due to the small chelate bite angle imposed by the rigid
o-phenylenediamine ligand backbone. Spectroscopic and magnetic studies of these complexes
are also described. The Cu(I)-carbonyl complexes [Cu(LMe)(CO)]PF6 and [Cu(Me6tren)(CO)]PF6
have been prepared. Infrared spectroscopy investigations of these carbonyl complexes not only
confirm that LMe is a less neucleophilic ligand but also exhibit different solution and solid-state
topologies. Finally, the reactivity of the [CuI(LMe)]+ with dioxygen and the resulting species
reactivity with C-H is bonds is described.

Synthesis and Reactivity of Transition Metal Complexes Supported by a Neutral Tetraamine
Ligand Containing N,N'-dimethylaniline Units
By
Lei Chu
B.S. University of Science and Technology, 2006
Advisor: Cora E. MacBeth, Ph.D.
A thesis submitted to the Faculty of the
James T. Laney School of Graduate Studies of Emory University
in partial fulfillment of the requirements for the degree of
Master of Science
in Chemistry
2010

Table of Contents

Table of Contents
Section















Page

List of Figures

List of Tables

List of Schemes

List of Charts

List of Abbreviations

Part I. Transition Metal Complexes Supported by a Neutral Tetraamine Ligand 1
Containing N,N'-dimethylaniline Units
Part I.I Introduction
1
Part I.II Results and Discussion
4
Part I.III X-ray Crystallographic Studies
5
Part I.IV Spectroscopic and Magnetic Properties of [MII(LMe)X]+ Complexes
13
Part I.V Cu(I) Carbonyl Complexes
15
Part I.VI Conclusions
19
Part II. Chemistry of Cu(I)-O2 Complexes supported by LMe
20
Part II.I Cu-O Derived Species and Biological Functions
20
Part II.II Cu-O Complexes for Aliphatic C-H Activation
21
Part II.III Results and Discussion
23
Part II.IV C-H Activation of Toluene
27
Part II.V Possible Mechanisms
27
Part II.VI Conclusions
29
Part III. Experimental Section
29
Part IV. References
44

About this Master's Thesis

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• Permission granted by the author to include this thesis or dissertation in this repository. All rights reserved by the author. Please contact the author for information regarding the reproduction and use of this thesis or dissertation.

School	Laney Graduate School
Department	Chemistry
Degree	MS
Submission	Master's Thesis
Language	English
Research Field	Chemistry, Inorganic
Palavra-chave	tetraamine, tripodal, five-coordinate metal halides, Cu(I)-carbonyl complexes
Committee Chair / Thesis Advisor	MacBeth, Cora, Emory University
Committee Members	Hill, Craig L, Emory University Blakey, Simon, Emory University

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