Synthesis, Characterization, and Catalytic Activities of A Nickel(II) Monoamido-Tetradentate Complex: Evidence For NiIII -Oxo and NiIV -Oxo Species

Abstract

A new mononuclear nickel(II) complex, [Ni^II (dpaq)Cl] (1), containing a tetradentate monoamido ligand, dpaq (dpaq=2-[bis(pyridin-2-ylmethyl)amino]-N-(quinolin-8-yl)acetamide), has been synthesized and characterized by IR spectroscopy, elemental analysis, and UV/Vis spectroscopy. The structure of the nickel complex has been determined by X-ray crystallography. This nonheme Ni^II complex 1 catalyzed the epoxidation reaction of a wide range of olefins with meta-chloroperoxybenzoic acid (m-CPBA) under mild conditions. Olefin epoxidation using this catalytic system has been proposed to involve a new reactive Ni^IV -oxo (4) species, based on the evidence from a PPAA (peroxyphenylacetic acid) probe, Hammett studies, H₂¹⁸ O exchange experiments, and ESI mass spectroscopic analysis. Moreover, the nature of solvent significantly influenced partitioning between heterolytic and homolytic O-O bond cleavage of the Ni-acylperoxo intermediate (2). The O-O bond of 2 proceeded predominantly through heterolytic cleavage in a protic solvent, such as CH₃ OH. These results suggest that possibly a Ni^IV -oxo species is a common reactive intermediate in protic solvents. The two active oxidants, namely Ni^IV -oxo (3) and Ni^III -oxo (4), which are responsible for stereospecific olefin epoxidation and radical-type oxidations, respectively, operate in aprotic solvents.

Keywords: epoxidation; nickel; nickel-oxo species; olefins; oxidation.