Synthesis, Characterization, and Dioxygen Reactivity of a Copper(I) Complex Supported by a Tripodal Tetraamine Ligand Open Access
Ando, Nicole Sets (2012)
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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