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Evidence for Bidirectional Noninnocent Behavior of a Formazanate Ligand in Ruthenium Complexes
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SYSNO ASEP 0446716 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Evidence for Bidirectional Noninnocent Behavior of a Formazanate Ligand in Ruthenium Complexes Author(s) Mandal, A. B. (IN)
Schwederski, B. (DE)
Fiedler, Jan (UFCH-W) RID, ORCID
Kaim, W. (DE)
Lahiri, G. K. (IN)Source Title Inorganic Chemistry. - : American Chemical Society - ISSN 0020-1669
Roč. 54, č. 16 (2015), s. 8126-8135Number of pages 10 s. Language eng - English Country US - United States Keywords ELECTRON-PARAMAGNETIC-RESONANCE ; DENSITY-FUNCTIONAL THEORY ; BORON DIFLUORIDE COMPLEXES Subject RIV CF - Physical ; Theoretical Chemistry R&D Projects GA14-05180S GA ČR - Czech Science Foundation (CSF) Institutional support UFCH-W - RVO:61388955 UT WOS 000359824400051 EID SCOPUS 84939449711 DOI 10.1021/acs.inorgchem.5b01408 Annotation Redox series of the complexes [Ru(L)(L′)2]n, L = 1,5-diphenyl-3-(4-tolyl)-formazanate and L′ = 2,4-pentanedionate (acac-), 2,2′-bipyridine (bpy), or 2-phenylazopyridine (pap), were studied by cyclic and differential pulse voltammetry and by TD-DFT-supported spectroelectrochemistry (UV-vis-NIR, EPR). The precursors [RuIII(L-)(acac-)2], [RuII(L-)(bpy)2]ClO4, and [RuII(L-)(pap)2]ClO4 were identified in their indicated oxidation states by X-ray crystal structure determination. The six-membered formazanato-ruthenium chelate rings have an envelope conformation with puckering of the metal. DFT calculations indicate a pronounced sensitivity of the N-N bond lengths toward the ligand oxidation state. Several electrochemically accessible charge states were analyzed, and the derived oxidation numbers RuII, RuIII, or RuIV, L′ or (L′)•-, and L-, L•2-, or the new formazanyl ligand L• for the two-way noninnocent formazanate reflect the increasing acceptor effect of the ancillary ligands L′ in the series acac- < bpy < pap. (Figure Presented). Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2016
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