Effect of Redox-Inactive Metal Ion-Nickel(III) Interactions on the Redox Properties and Proton-Coupled Electron Transfer Reactivity

Abstract

Mononuclear nickel(II) and nickel(III) complexes of a bisamidate-bisalkoxide ligand, (NMe₄)₂[Ni^II(HMPAB)] (1) and (NMe₄)[Ni^III(HMPAB)] (2), respectively, have been synthesized and characterized by various spectroscopic techniques including X-ray crystallography. The reaction of redox-inactive metal ions (Mⁿ⁺ = Ca²⁺, Mg²⁺, Zn²⁺, Y³⁺, and Sc³⁺) with 2 resulted in 2-Mⁿ⁺ adducts, which was assessed by an array of spectroscopic techniques including X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR), and reactivity studies. The X-ray structure of Ca²⁺ coordinated to Ni(III) complexes, 2-Ca²⁺T, was determined and exhibited an average Ni-Ca distance of 3.1253 Å, close to the metal ions' covalent radius. XAS analysis of 2-Ca²⁺ and 2-Y³⁺ in solution further revealed an additional coordination to Ca and Y in the 2-Mⁿ⁺ adducts with shortened Ni-M distances of 2.15 and 2.11 Å, respectively, implying direct bonding interactions between Ni and Lewis acids (LAs). Such a short interatomic distance between Ni(III) and M is unprecedented and was not observed before. EPR analysis of 2 and 2-Mⁿ⁺ species, moreover, displayed rhombic signals with g_av > 2.12 for all complexes, supporting the +III oxidation state of Ni. The Ni^III/Ni^II redox potential of 2 and 2-Mⁿ⁺ species was determined, and a plot of E_1/2 of 2-Mⁿ⁺ versus pK_a of [M(H₂O)_n]^m+ exhibited a linear relationship, implying that the Ni^III/Ni^II potential of 2 can be tuned with different redox-inactive metal ions. Reactivity studies of 2 and 2-Mⁿ⁺ with different 4-X-2,6-ditert-butylphenol (4-X-DTBP) and other phenol derivatives were performed, and based on kinetic studies, we propose the involvement of a proton-coupled electron transfer (PCET) pathway. Analysis of the reaction products after the reaction of 2 with 4-OMe-DTBP showed the formation of a Ni(II) complex (1a) where one of the alkoxide arms of the ligand is protonated. A pK_a value of 24.2 was estimated for 1a. The reaction of 2-Mⁿ⁺ species was examined with 4-OMe-DTBP, and it was observed that the k₂ values of 2-Mⁿ⁺ species increase by increasing the Lewis acidity of redox-inactive metal ions. However, the obtained k₂ values for 2-Mⁿ⁺ species are much lower compared to the k₂ value for 2. Such a variation of PCET reactivity between 2 and 2-Mⁿ⁺ species may be attributed to the interactions between Ni(III) and LAs. Our findings show the significance of the secondary coordination sphere effect on the PCET reactivity of Ni(III) complexes and furnish important insights into the reaction mechanism involving high-valent nickel species, which are frequently invoked as key intermediates in Ni-mediated enzymatic reactions, solar-fuel catalysis, and biomimetic/synthetic transformation reactions.