Electronically Strongly Coupled Divinylheterocyclic-Bridged Diruthenium Complexes

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PFAFF, Ulrike, Alexander HILDEBRANDT, Marcus KORB, Steffen OSSWALD, Michael LINSEIS, Katja SCHREITER, Stefan SPANGE, Rainer F. WINTER, Heinrich LANG, 2016. Electronically Strongly Coupled Divinylheterocyclic-Bridged Diruthenium Complexes. In: Chemistry - A European Journal. 22(2), pp. 783-801. ISSN 0947-6539. eISSN 1521-3765

@article{Pfaff2016Elect-32726, title={Electronically Strongly Coupled Divinylheterocyclic-Bridged Diruthenium Complexes}, year={2016}, doi={10.1002/chem.201503687}, number={2}, volume={22}, issn={0947-6539}, journal={Chemistry - A European Journal}, pages={783--801}, author={Pfaff, Ulrike and Hildebrandt, Alexander and Korb, Marcus and Oßwald, Steffen and Linseis, Michael and Schreiter, Katja and Spange, Stefan and Winter, Rainer F. and Lang, Heinrich} }

<rdf:RDF xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:dcterms="http://purl.org/dc/terms/" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/32726"> <dc:contributor>Winter, Rainer F.</dc:contributor> <dc:contributor>Schreiter, Katja</dc:contributor> <dc:contributor>Hildebrandt, Alexander</dc:contributor> <dc:creator>Schreiter, Katja</dc:creator> <dc:contributor>Linseis, Michael</dc:contributor> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2016-01-26T14:39:56Z</dc:date> <dcterms:abstract xml:lang="eng">Complexes [{Ru(CO)Cl(PiPr3 )2 }2 (μ-2,5-(CHCH)2 -(c) C4 H2 E] (E=NR; R=C6 H4 -4-NMe2 (10 a), C6 H4 -4-OMe (10 b), C6 H4 -4-Me (10 c), C6 H5 (10 d), C6 H4 -4-CO2 Et (10 e), C6 H4 -4-NO2 (10 f), C6 H3 -3,5-(CF3 )2 (10 g), CH3 (11); E=O (12), S (13)) are discussed. The solid state structures of four alkynes and two complexes are reported. (Spectro)electrochemical studies show a moderate influence of the nature of the heteroatom and the electron-donating or -withdrawing substituents R in 10 a-g on the electrochemical and spectroscopic properties. The CVs display two consecutive one-electron redox events with ΔE°'=350-495 mV. A linear relationship between ΔE°' and the σp Hammett constant for 10 a-f was found. IR, UV/Vis/NIR and EPR studies for 10(+) -13(+) confirm full charge delocalization over the {Ru}CHCH-heterocycle-CHCH{Ru} backbone, classifying them as Class III systems according to the Robin and Day classification. DFT-optimized structures of the neutral complexes agree well with the experimental ones and provide insight into the structural consequences of stepwise oxidations.</dcterms:abstract> <bibo:uri rdf:resource="https://kops.uni-konstanz.de/handle/123456789/32726"/> <dc:contributor>Oßwald, Steffen</dc:contributor> <dcterms:title>Electronically Strongly Coupled Divinylheterocyclic-Bridged Diruthenium Complexes</dcterms:title> <dc:creator>Spange, Stefan</dc:creator> <dc:creator>Linseis, Michael</dc:creator> <dc:contributor>Pfaff, Ulrike</dc:contributor> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2016-01-26T14:39:56Z</dcterms:available> <dc:creator>Lang, Heinrich</dc:creator> <dc:creator>Korb, Marcus</dc:creator> <dc:creator>Hildebrandt, Alexander</dc:creator> <dcterms:issued>2016</dcterms:issued> <dc:creator>Winter, Rainer F.</dc:creator> <dc:contributor>Spange, Stefan</dc:contributor> <dc:contributor>Lang, Heinrich</dc:contributor> <dc:creator>Pfaff, Ulrike</dc:creator> <dc:language>eng</dc:language> <dc:creator>Oßwald, Steffen</dc:creator> <dc:contributor>Korb, Marcus</dc:contributor> </rdf:Description> </rdf:RDF>

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