Abstract
Ligand design is an area of great interest to chemists. With
respect to coordination chemistry, ligands may be tailored
sterically, electronically, and through installation of
functionalities that make up the secondary coordination sphere of
the transition metal ion. In Chapter 2 of this dissertation, the
synthesis of a series of tetradentate ligands that vary in the
electronic character of the aromatic acyl substituent is described.
Cobalt(II) complexes of these ligands were prepared, and their
synthesis and characterization will also be discussed. The cyanide
binding properties of these complexes were explored, and it was
found that the complexes with the most electron- withdrawing
substituents not only effect the most electron-poor cobalt center,
but they also appear to effect a type of secondary interaction
between the bound cyanide and the aromatic rings that has not yet
been described in the literature. In Chapter 3, the synthesis,
characterization, and reactivity of iron(II) complexes that utilize
similar ligands will be explored. Several of the complexes with
electron-rich aromatic acyl substituents have proven to be
effective catalysts for N-methyl C-H bond activation. The catalytic
activity and proposed mechanism of action will be discussed. A
byproduct of this reaction, a rare, terminal Fe(II)-hemiaminate
species was isolated, and its characterization will also be
discussed. In Chapter 4, the synthesis, characterization, and
reactivity of cobalt(II), copper(I), and zinc(II) complexes of a
neutral, tridentate ligand will be described. These complexes have
the potential to be useful as low coordinate, reactive transition
metal complexes.
Table of Contents
Table of Contents
Chapter 1 Ligand Design Strategies for Regulating Small Molecule
Binding and
Reactivity at Transition Metal
Centers………………………………………..1
Section 1-1
Introduction……………………………………………………………………….1
Section 1-2 Utility of Ligand Design in Tetradentate Triamidoamine
Ligands………………2
Section 1-3 Ligand Design in Tetradentate Tris(carboxamide)amine
Ligands……………….8
Section 1-4 Dissertation
Overview…………………………………………………..............11
Chapter 2 Utilizing Aromatic Substituents for Regulation of
Cyanide Binding by
Cobalt(II) Metal
Complexes…………………………………………………..16
Section 2-1
Introduction……………………………………………………………………...16
Section 2-2 Results and
Discussion………………………………………………………….26
Section 2-2-1 Synthesis of Trigonal Monopyramidal and Solvento
Cobalt(II)
Complexes………………………………………………………………………27
Section 2-2-2 Structural Characterization of Trigonal Monopyramidal
and Solvento
Cobalt(II)
Complexes…………………………………………………………...31
Section 2-2-3 Cyanide
Binding………………………………………………………………...37
Section 2-2-4 Electrochemistry and Alkyl-Substituted
Complexes…………………………...49
Section 2-3
Conclusion……………………………………………………………………...54
Section 2-4 Experimental
Section…………………………………………………………...56
Chapter 3 Biomimetic Aerobic Oxidation of N-alkyl C-H Bonds by
a
Non-heme Iron(II)
Catalyst…………………………………………………...89
Section 3-1
Introduction……………………………………………………………………..89
Section 3-2 Background and
Significance……………………………………………….…..94
Section 3-2 Results and
Discussion………………………………………………………...100
Section 3-3
Conclusion……………………………………………………………………..130
Section 3-4 Experimental
Section………………………………………………….............130
Chapter 4 Use of a Neutral, Tridentate Ligand for Stabilization
of Low
Coordinate Transition Metal
Complexes…………………………………...154
Section 4-1
Introduction…………………………………………………………………….154
Section 4-2 Results and
Discussion………………………………………………………...161
Section 4-3
Conclusion……………………………………………………………..............177
Section 4-4 Experimental
Section…………………………………………………………..178
About this Dissertation
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