C-H Bond Activation by a Mononuclear Nickel(IV)-Nitrate Complex

Yubin M. Kwon, Yuri Lee, Anna K. Schmautz, Timothy A. Jackson, Dong Wang

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

The recent focus on developing high-valent non-oxo-metal complexes for late transition metals has proven to be an effective strategy to study the rich chemistry of these high-valent species while bypassing the synthetic challenges of obtaining the oxo-metal counterparts. In our continuing work of exploring late transition metal complexes of unusually high oxidation states, we have obtained in the present study a formal mononuclear Ni(IV)-nitrate complex (2) upon 1-e-oxidation of its Ni(III) derivatives (1-OH and 1-NO3). Characterization of these Ni complexes by combined spectroscopic and computational approaches enables deep understanding of their geometric and electronic structures, bonding interactions, and spectroscopic properties, showing that all of them are square planar complexes and exhibit strong π-covalency with the amido N-donors of the N3 ligand. Furthermore, results obtained from X-ray absorption spectroscopy and density functional theory calculations provide strong support for the assignment of the Ni(IV) oxidation state of complex 2, albeit with strong ligand-to-metal charge donation. Notably, 2 is able to oxidize hydrocarbons with C-H bond strength in the range of 76-92 kcal/mol, representing a rare example of high-valent late transition metal complexes capable of activating strong sp3C-H bonds.

Original languageEnglish
Pages (from-to)12072-12080
Number of pages9
JournalJournal of the American Chemical Society
Volume144
Issue number27
DOIs
StatePublished - Jul 13 2022

Fingerprint

Dive into the research topics of 'C-H Bond Activation by a Mononuclear Nickel(IV)-Nitrate Complex'. Together they form a unique fingerprint.

Cite this