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Synthesis and Characterization of a Masked Terminal Nickel-Oxide Complex

Heim, P.; Spedalotto, G.; Lovisari, M.; Gericke, R.; O’Brien, J.; Farquhar, E. R.; McDonald, A. R.


In exploring terminal nickel-oxo complexes, postulated to be the active oxidant in natural and non-natural oxidation reactions, we report the synthesis of the pseudo-trigonal bipyramidal Ni(II) complexes (K)[Ni(II)(LPh)(DMF)] (1[DMF]) and (NMe₄)₂[Ni(II)(LPh)(OAc)] (1[OAc]) (LPh = 2,2’,2’’-nitrilo-tris-(N-phenylacetamide); DMF = N,N-dimethylformamide; OAc = acetate). Both complexes were characterized using NMR, FTIR, ESI-MS, and X-ray crystallography, showing the LPh ligand to bind in a tetradentate fashion, together with an ancillary donor. The reaction of 1[OAc] with peroxyphenyl acetic acid (PPAA) resulted in the formation of [(LPh)Ni(III)-O-H···OAc]²-, 2, that displays many of the characteristics of a terminal Ni=O species. 2 was characterized by UV-Vis, EPR, and XAS spectroscopies and ESI-MS. 2 decayed to yield a Ni(II)-phenolate complex 3 (through aromatic electrophilic substitution) that was characterized by NMR, FTIR, ESI-MS, and X-ray crystallography. 2 was capable of hydroxylation of hydrocarbons and epoxidation of olefins, as well as oxygen atom transfer oxidation of phosphines at exceptional rates. While the oxo-wall remains standing, this complex represents an excellent example of a masked metal-oxide that displays all of the properties expected of the ever elusive terminal M=O beyond the oxo-wall.

Keywords: bioinorganic chemistry; high-valent nickel; hydrocarbon oxidation; oxo-wall; peracid activation