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Evidence for the dimer-of-(mixed-valent dimers) configuration in tetranuclear {(mu(4)-TCNX)[Ru(NH3)(5)](4)}(8+), TCNX = TCNE and TCNQ, from DFT calculations
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SYSNO ASEP 0335779 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Evidence for the dimer-of-(mixed-valent dimers) configuration in tetranuclear {(mu(4)-TCNX)[Ru(NH3)(5)](4)}(8+), TCNX = TCNE and TCNQ, from DFT calculations Title Evidence konfigurace Dimer- (dimery se smíšenou valencí) ve čtyřjaderném komplexu {(mu(4)-TCNX)[Ru(NH3)(5)](4)}(8+), TCNX = TCNE a TCNQ, na základě DFT výpočtů Author(s) Záliš, Stanislav (UFCH-W) RID, ORCID
Sarkar, B. (DE)
Duboc, C. (FR)
Kaim, A. (DE)Source Title Monatshefte fur Chemie. - : Springer - ISSN 0026-9247
Roč. 140, č. 7 (2009), s. 765-773Number of pages 9 s. Language eng - English Country AT - Austria Keywords Density functional calculations ; Transition metal compounds ; Ruthenium complexes ; redox states Subject RIV CG - Electrochemistry R&D Projects OC 139 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) KAN100400702 GA AV ČR - Academy of Sciences of the Czech Republic (AV ČR) CEZ AV0Z40400503 - UFCH-W (2005-2011) UT WOS 000266926500005 DOI 10.1007/s00706-009-0129-3 Annotation DFT calculations of the complex ions {(mu(4)-TCNX)[Ru(NH3)(5)](4)}(8+), TCNX = tetracyanoethene (TCNE) and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ), yield triplet state energy minimum structures with nonplanar bridging ligands. The calculated C-C bond distances and twist angles confirm considerable metal-to-ligand electron transfer from the metal centers to the TCNE and TCNQ bridges in the lowest triplet and singlet states. The resulting situation, involving a weak interaction between two strongly coupled malonodinitrilato-bridged (RuRu2.5)-Ru-2.5 entities (Class III), agrees with experimental results; the near-orthogonality found for the ground states of the molecular ions explains the observed magnetic exchange coupling between two S = 1/2 sites, the 1,258 cm(-1) absorption in the IR spectrum of the TCNE complex, and the reversible two-electron oxidation. The nitrile stretching frequency shifts were reasonably reproduced by the calculations. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2010
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