Synthesis, Characterization, and Dioxygen Reactivity of a Copper(I) Complex Supported by a Tripodal Tetraamine Ligand Open Access

Ando, Nicole Sets (2012)

Permanent URL: https://etd.library.emory.edu/concern/etds/j098zb69d?locale=en
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Abstract

In this manuscript, the tripodal tetradentate ligand tris(2-dimethylaminophenyl)amine (LMe) has been prepared and shown to be less electron donating than the other commonly employed tetradentate ligands tris(N,N-dimethylaminoethyl)amine (Me6tren) and tris(2-pyridylmethyl)amine (tmpa). The ligand LMe can be metallated with a copper(I) source to yield the corresponding mononuclear complex, [CuI(LMe)(CH3CN)]PF6. When [CuI(LMe)(CH3CN)]PF6 is exposed to dioxygen in a solution of acetone at low temperature (-78 oC), it readily reacts to produce a dicopper(II) trans-μ-1,2-peroxo complex, [CuII2(LMe)2(μ-1,2-O2)](PF6)2. This complex has been characterized by resonance Raman and UV-visible absorption spectroscopies and is compared to predeceasing dicopper(II) trans-μ-1,2-peroxo complexes. The decayed product of [CuII2(LMe)2(μ-1,2-O2)](PF6)2 has been isolated and characterized as he mononuclear terminal hydroxide complex [CuII(LMe)(OH)]PF6. The reactivity of [CuII2(LMe)2(μ-1,2-O2)](PF6) towards the aerobic oxidation of toluene to benzaldehyde is also described.

Table of Contents

Table of Contents Section Page

List of Figures

List of Tables

List of Schemes

List of Charts

List of Abbreviations

I. Introduction 1

II. Results and Discussion 7

Synthesis and Characterization of CuI Complexes 7

Electronic Studies of the Ligand N(o-PhNMe2)3 9

Reactivity of CuI Complexes Binding to Dioxygen 13

Decay of CuII-peroxo Complexes to CuII-OH Complexes 17

Reactivity of CuII-peroxo Complexes with Toluene 18

Reactivity of CuII-peroxo Complexes with Alternative Substrates 22

III. Conclusion 24

IV. Experimental 26

V. Crystallographic Data 33

VI. References 37

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