Publication Date

2013-07-10

Availability

Open access

Embargo Period

2013-07-10

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PHD)

Department

Chemistry (Arts and Sciences)

Date of Defense

2013-04-09

First Committee Member

Carl D. Hoff

Second Committee Member

Burjor Captain

Third Committee Member

Angel Kaifer

Fourth Committee Member

Manuel Temprado

Abstract

Oxygen activation and binding to two transition-metal systems: late transition-metal system Pd(L1)(L2) (L1= NHC, L2= NHC or PR3) and early transition-metal system V(N(tBu)Ar)3 (Ar = 3,5-Me2C6H3) was explored in order to gain information about the thermodynamics, kinetics and mechanism of O2 binding to metal complexes. In this work, a novel oxygen binding mode was discovered and the resulting complex Pd(IPr)2(η1-O2)2 was reported as the first η1 oxygenation palladium complex. This reaction was further studied and a plausible mechanism of O2 binding to Pd(L1)(L2) system was proposed, in which the effect of ligands bulkiness and an equilibrium between η1-Pd and η2-Pd were highlighted. In addition, an early transition-metal peroxo complex V(N(tBu)Ar)3(η2-O2) has been prepared directly by reaction with O2. Its equilibrium with V(N(tBu)Ar)3(η1-O2) and its reactivity were investigated. Finally the binding and activation of a potent oxygen atom transfer reagent MesCNO were studied.

Keywords

oxygen atom transfer; selective oxidation; palladium carbene; mechanism; thermodynamic; kinetic

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