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

Mononuclear nickel(II) and nickel(III) complexes of a bisamidate-bisalkoxide ligand, (NMe 4 ) 2 [Ni II (HMPAB)] ( 1 ) and (NMe 4 )[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 (M n + = Ca 2+ , Mg 2+ , Zn 2+ , Y 3+ , and Sc 3+ ) with 2 resulted in 2 -M n + 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 Ca 2+ coordinated to Ni(III) complexes, 2 -Ca 2+ 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 -Ca 2+ and 2 -Y 3+ in solution further revealed an additional coordination to Ca and Y in the 2 -M n + 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 -M n + 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 -M n + species was determined, and a plot of E 1/2 of 2 -M n + versus p K a of [M(H 2 O) 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 -M n + with different 4-X-2,6-di tert -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 p K a value of 24.2 was estimated for 1a . The reaction of 2 -M n + species was examined with 4-OMe-DTBP, and it was observed that the k 2 values of 2 -M n + species increase by increasing the Lewis acidity of redox-inactive metal ions. However, the obtained k 2 values for 2 -M n + species are much lower compared to the k 2 value for 2 . Such a variation of PCET reactivity between 2 and 2 -M n + 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.