Improved Oxidative C-C Bond Formation Reactivity of High-Valent Pd Complexes Supported by a Pseudo-Tridentate Ligand

There is a large interest in developing oxidative transformations catalyzed by palladium complexes that employ environmentally friendly and economical oxidizing reagents such as dioxygen. Recently, we have reported the isolation and characterization of various mononuclear Pd^III and Pd^IV complexes supported by the tetradentate ligands N,N'-dialkyl-2,11-diaza[3.3](2,6)pyridinophane (^RN4, R = ^tBu, ⁱPr, Me), and the aerobically induced C-C and C-heteroatom bond formation reactivity was investigated in detail. Given that the steric and electronic properties of the multidentate ligands were shown to tune the stability and reactivity of the corresponding high-valent Pd complexes, herein we report the use of an asymmetric N4 ligand, N-mehtyl-N'-tosyl-2,11-diaza[3.3](2,6)pyridinophane (^TsMeN4), in which one amine N atom contains a tosyl group. The N-Ts donor atom exhibits a markedly reduced donating ability, which led to the formation of transiently stable Pd^III and Pd^IV complexes, and consequently the corresponding O₂ oxidation reactivity and the subsequent C-C bond formation were improved significantly.