Type of Publication: | Journal article |
Publication status: | Published |
Author: | Pfaff, Ulrike; Hildebrandt, Alexander; Korb, Marcus; Oßwald, Steffen; Linseis, Michael; Schreiter, Katja; Spange, Stefan; Winter, Rainer F.; Lang, Heinrich |
Year of publication: | 2016 |
Published in: | Chemistry - A European Journal ; 22 (2016), 2. - pp. 783-801. - ISSN 0947-6539. - eISSN 1521-3765 |
Pubmed ID: | 26660031 |
DOI (citable link): | https://dx.doi.org/10.1002/chem.201503687 |
Summary: |
Complexes [{Ru(CO)Cl(PiPr3 )2 }2 (μ-2,5-(CHCH)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}CHCH-heterocycle-CHCH{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.
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Subject (DDC): | 540 Chemistry |
Bibliography of Konstanz: | Yes |
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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. Available under: doi: 10.1002/chem.201503687
@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} }
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