Altering the Localization of an Unpaired Spin in a Formal Ni(V) Species.

Autor: Awasthi A; Southern Laboratories-208 A, Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, India., Mallojjala SC; Department of Chemistry, Binghamton University, Binghamton, New York, 13902, USA., Kumar R; Southern Laboratories-208 A, Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, India., Eerlapally R; Southern Laboratories-208 A, Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, India., Hirschi JS; Department of Chemistry, Binghamton University, Binghamton, New York, 13902, USA., Draksharapu A; Southern Laboratories-208 A, Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, India.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Jan 16; Vol. 30 (4), pp. e202302824. Date of Electronic Publication: 2023 Nov 27.
DOI: 10.1002/chem.202302824
Abstrakt: The participation of both ligand and the metal center in the redox events has been recognized as one of the ways to attain the formal high valent complexes for the late 3d metals, such as Ni and Cu. Such an approach has been employed successfully to stabilize a Ni(III) bisphenoxyl diradical species in which there exist an equilibrium between the ligand and the Ni localized resultant spin. The present work, however, broadens the scope of the previously reported three oxidized equivalent species by conveying the approaches that tend to affect the reported equilibrium in CH 3 CN at 233 K. Various spectroscopic characterization revealed that employing exogenous N-donor ligands like 1-methyl imidazole and pyridine favors the formation of the Ni centered localized spin though axial binding. In contrast, due to its steric hinderance, quinoline favors an exclusive ligand localized radical species. DFT studies shed light on the novel intermediates' complex electronic structure. Further, the three oxidized equivalent species with the Ni centered spin was examined for its hydrogen atom abstraction ability stressing their key role in alike reactions.
(© 2023 Wiley-VCH GmbH.)
Databáze: MEDLINE
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