A Bis(μ-oxido)dinickel(III) Complex with a Triplet Ground State

Yuma Morimoto; Yusaku Takagi; Toru Saito; Takehiro Ohta; Takashi Ogura; Norimitsu Tohnai; Motohiro Nakano; Shinobu Itoh

doi:10.1002/anie.201802779

A Bis(μ-oxido)dinickel(III) Complex with a Triplet Ground State

Angew Chem Int Ed Engl. 2018 Jun 25;57(26):7640-7643. doi: 10.1002/anie.201802779. Epub 2018 May 22.

Authors

Yuma Morimoto¹, Yusaku Takagi¹, Toru Saito², Takehiro Ohta³, Takashi Ogura³, Norimitsu Tohnai¹, Motohiro Nakano⁴, Shinobu Itoh¹

Affiliations

¹ Department of Material and Life Science, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan.
² Department of Biomedical Information Sciences, Graduate School of Information Sciences, Hiroshima City University, 3-4-1 Ozuka-Higashi, Asa-Minami-Ku, Hiroshima, 731-3194, Japan.
³ Picobiology Institute, Graduate School of Life Science, University of Hyogo, RSC-UH LP Center, 1-1-1 Koto, Sayo-cho, Sayo-gun, Hyogo, 679-5148, Japan.
⁴ Research Center for Structural Thermodynamics, Graduate School of Science, Osaka University, 1-1 Machikaneyama-cho, Toyonaka, Osaka, 560-0043, Japan.

PMID: 29693754
DOI: 10.1002/anie.201802779

Abstract

A bis(μ-oxido)dinickel(III) complex was synthesized and characterized by single crystal X-ray diffraction, resonance Raman, and ESI-mass measurements. Magnetic susceptibility measurements by SQUID and EPR spectroscopy reveal that the complex has a triplet ground state, which is unprecedented for high-valent metal (M) complexes with [M₂ (μ-O)₂ ] diamond core. DFT studies indicate ferromagnetic coupling of the nickel(III) centers. The complex exhibits hydrogen abstraction reactivity and oxygenation reactivity toward external substrates.

Keywords: bis(μ-oxido) complexes; magnetic properties; nickel; oxidation; reactive intermediates.

Publication types

Research Support, Non-U.S. Gov't