4.8 Article

Trapping of the putative 1,2-dinitrosoarene intermediate of benzofuroxan tautomerization by coordination at ruthenium and exploration of its redox non-innocence

期刊

CHEMICAL SCIENCE
卷 5, 期 10, 页码 3883-3887

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ROYAL SOC CHEMISTRY
DOI: 10.1039/c4sc01185f

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  1. Hong Kong Research Grants Council [CityU 103911]
  2. City University of Hong Kong [7004022]
  3. Max Planck Society

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The reaction of a benzofuroxan with [Ru([9]aneS3)(dmso)Cl-2] ([9] aneS3 = 1,4,7-trithiacyclononane) and [Ru(bpy)(2)(CH3CN)(2)](2+) yields the ruthenium complexes [Ru([9]aneS3)((ONNO)-N-boolean AND)(Cl)](+) (1a-c) and [Ru(bpy)(2)((ONNO)-N-boolean AND)](n+) (n = 2: 2a and 2b; n = 1: 2a(-) and 2b(-)), respectively, containing neutral or monoanionic N, N'-coordinated 1,2-dinitrosoarenes ((ONNO)-N-boolean AND). The oxidation states of the (ONNO)-N-boolean AND ligands (0 for 1a-c, 2a and 2b; -1 for 2a(-) and 2b(-)) have been deduced through detailed structural, spectroscopic, and theoretical studies. In other words, not only does this work demonstrate the trapping of the putative 1,2-dinitrosoarene intermediate of benzofuroxan tautomerization by coordination to ruthenium, it also provides access to a new family of redox-active bidentate ligands.

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