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- Title
Redox Non‐Innocence of ortho‐Benzoquinone Dioximate Dianion in Ligand Exchange on Ruthenium.
- Authors
Harada, Takuya; Ando, Shinji; Kuwata, Shigeki
- Abstract
A ruthenium complex bearing an o‐benzoquinone dioximate dianion was isolated, and its ligand‐based redox chemistry was clarified. The reaction of [Cp*RuCl2(NO)] (Cp*=η5‐C5Me5) with o‐benzoquinone dioxime (LredH2) in the presence of a base afforded a dioximato ruthenium complex [Cp*Ru(NO)(Lred)] (1). Upon treatment with an iodonium salt, 1 underwent two‐electron oxidation of Lred along with ligand exchange to give the o‐dinitrosobenzene (Lox) iodido complex [Cp*RuI(Lox)] (2). 1H NMR, IR, X‐ray analyses, and DFT calculations revealed that the Lred ligand in 1 was oxidized and aromatized during the ligand substitution. The Lox ligand in 2 was reduced by benzensulfohydroxamic acid with the aid of a base, leading to regeneration of the Lred nitrosyl complex 1. The non‐innocence of Lred/ox in the ligand exchange would lead to level the energy profile of redox processes including catalysis.
- Subjects
NITROSYL compounds; RUTHENIUM; DIANIONS; OXIDATION-reduction reaction; RUTHENIUM compounds; IODONIUM salts
- Publication
European Journal of Inorganic Chemistry, 2022, Vol 2022, Issue 25, p1
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.202200293