Aromatic and aliphatic hydrocarbon hydroxylation via a formally NiIVO oxidant.

The reaction of (NMe4)2[NiII(LPh)(OAc)] (1[OAc], LPh = 2,2',2''-nitrilo-tris-(N-phenylacetamide); OAc = acetate) with 3-chloroperoxybenzoic acid (m-CPBA) resulted in the formation of a self-hydroxylated NiIII-phenolate complex, 2, where one of the phenyl groups of LPh underwent hydroxylation. 2 was characterised by UV-Vis, EPR, and XAS spectroscopies and ESI-MS. 2 decayed to yield a previously characterised NiII-phenolate complex, 3. We postulate that self-hydroxylation was mediated by a formally NiIVO oxidant, formed from the reaction of 1[OAc] with m-CPBA, which undergoes electrophilic aromatic substitution to yield 2. This is supported by an analysis of the kinetic and thermodynamic properties of the reaction of 1[OAc] with m-CPBA. Addition of exogenous hydrocarbon substrates intercepted the self-hydroxylation process, producing hydroxylated products, providing further support for the formally NiIVO entity. This study demonstrates that the reaction between NiII salts and m-CPBA can lead to potent metal-based oxidants, in contrast to recent studies demonstrating carboxyl radical is a radical free-chain reaction initiator in NiII/m-CPBA hydrocarbon oxidation catalysis.

Synthesis and Characterization of a Masked Terminal Nickel-Oxide Complex.

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 NiII complexes (K)[NiII (LPh )(DMF)] (1[DMF]) and (NMe4 )2 [NiII (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 )NiIII -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 NiII -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.

Reactivity Properties of Mixed- and High-Valent Bis(µ-Hydroxide)-Dinickel Complexes.

Despite their potential role in enzymatic systems, there is a dearth of hydroxide-bridged high-valent oxidants. We recently reported the synthesis and characterization of NiIINiIII(µ-OH)2 (2) and Ni2 III(µ-OH)2 (3) species supported by a dicarboxamidate ligand (N,N'-bis(2,6-dimethyl-phenyl)-2,2-dimethylmalonamide). Herein, we explore the oxidative reactivity of these species using a series of para-substituted 2,6-di-tert-butyl-phenols (4-X-2,6-DTBP, X = -OCH3, -CH2CH3, -CH3, -C(CH3)3, -H, -Br, -CN, and -NO2) as a mechanistic probe. Interestingly, upon reaction of 3 with the substrates, the formation of a new transient species, 2', was observed. 2' is postulated to be a protic congener of 2. All three species were demonstrated to react with the substituted phenols through a hydrogen atom transfer reaction mechanism, which was elucidated further by analysis of the postreaction mixtures. Critically, 3 was demonstrated to react at far superior rates to 2 and 2', and oxidized substrates more efficiently than any bis-µ-oxo-Ni2 III reported to date. The kinetic superiority of 3 with respect to 2 and 2' was attributed to a stronger bond in the product of oxidation by 3 when compared to those calculated for 2 and 2'.

Preparation and Characterisation of a Bis-µ-Hydroxo-NiIII 2 Complex.

Hydroxide-bridged high-valent oxidants have been implicated as the active oxidants in methane monooxygenases and other oxidases that employ bimetallic clusters in their active site. To understand the properties of such species, bis-µ-hydroxo-NiII 2 complex (1) supported by a new dicarboxamidate ligand (N,N'-bis(2,6-dimethyl-phenyl)-2,2-dimethylmalonamide) was prepared. Complex 1 contained a diamond core made up of two NiII ions and two bridging hydroxide ligands. Titration of the 1 e- oxidant (NH4 )2 [CeIV (NO3 )6 ] with 1 at -45 °C showed the formation of the high-valent species 2 and 3, containing NiII NiIII and NiIII 2 diamond cores, respectively, maintaining the bis-µ-hydroxide core. Both complexes were characterised using electron paramagnetic resonance, X-ray absorption, and electronic absorption spectroscopies. Density functional theory computations supported the spectroscopic assignments. Oxidation reactivity studies showed that bis-µ-hydroxide-NiIII 2 3 was capable of oxidizing substrates at -45 °C at rates greater than that of the most reactive bis-µ-oxo-NiIII complexes reported to date.