High-Valent Ni and Cu Complexes of a Tetraanionic Bis(amidateanilido) Ligand.

Abstract

High-valent metal species are often invoked as intermediates during enzymatic and synthetic catalytic cycles. Anionic donors are often required to stabilize such high-valent states by forming strong bonds with the Lewis acidic metal centers while decreasing their oxidation potentials. In this report, we discuss the synthesis of two high-valent metal complexes [ML]+ in which the NiIII and CuIII centers are ligated by a new tetradentate, tetraanionic bis(amidateanilido) ligand. [ML]+, obtained via chemical oxidation of ML, exhibits UV-vis-NIR, EPR, and XANES spectra characteristic of square planar, high-valent MIII species, suggesting the locus of oxidation for both [ML]+ is predominantly metal-based. This is supported by theoretical analyses, which also support the observed visible transitions as ligand-to-metal charge transfer transitions characteristic of square planar, high-valent MIII species. Notably, [ML]+ can also be obtained via O2 oxidation of ML due to its remarkably negative oxidation potentials (CuL/[CuL]+: -1.16 V, NiL/[NiL]+: -1.01 V vs Fc/Fc+ in MeCN). This demonstrates the exceptionally strong donating nature of the tetraanionic bis(amidateanilido) ligation and its ability to stabilize high-valent metal centers..