Vinyl ruthenium-modified biphenyl and 2,2'-bipyridines
We report here on ruthenium alkenyl complexes 2 and 3 derived from 2,2'-bipyridine and their Re(CO)3X adducts 4a,b and 5. Detailed electrochemical studies on these complexes and spectroscopic characterization of their oxidized forms by IR, UV/vis/NIR, and electron paramagnetic resonance spectro...
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| Vydáno v: | Inorganic chemistry Ročník 54; číslo 7; s. 3387 |
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| Hlavní autoři: | , , , , , , , |
| Médium: | Journal Article |
| Jazyk: | angličtina |
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United States
06.04.2015
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| ISSN: | 1520-510X, 1520-510X |
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| Abstract | We report here on ruthenium alkenyl complexes 2 and 3 derived from 2,2'-bipyridine and their Re(CO)3X adducts 4a,b and 5. Detailed electrochemical studies on these complexes and spectroscopic characterization of their oxidized forms by IR, UV/vis/NIR, and electron paramagnetic resonance spectroscopies as well as quantum chemical studies reveal sizable (bridging) ligand contributions to the redox orbitals. Engagement of the free bipy functions of complexes 2 and 3 in binding to the electron-withdrawing fac-Re(CO)3X (X = Br, Cl) moiety enhances the metal-to-ligand charge-transfer character of the optical excitations, causes sizable anodic shifts of the redox potentials, and decreases the number of observable anodic redox waves by one when compared to complexes 2 and 3. Despite the decreasing electron density at the terminal or bridging alkenyl bipyridine ligand, the anodic redox processes still maintain appreciable ligand character as is seen by the shifts of the Ru(CO) and Re(CO)3 stretching frequencies on oxidation. Binding of the fac-Re(CO)3X moiety also attenuates the degree of ground-state delocalization in the mixed-valent states. |
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| AbstractList | We report here on ruthenium alkenyl complexes 2 and 3 derived from 2,2'-bipyridine and their Re(CO)3X adducts 4a,b and 5. Detailed electrochemical studies on these complexes and spectroscopic characterization of their oxidized forms by IR, UV/vis/NIR, and electron paramagnetic resonance spectroscopies as well as quantum chemical studies reveal sizable (bridging) ligand contributions to the redox orbitals. Engagement of the free bipy functions of complexes 2 and 3 in binding to the electron-withdrawing fac-Re(CO)3X (X = Br, Cl) moiety enhances the metal-to-ligand charge-transfer character of the optical excitations, causes sizable anodic shifts of the redox potentials, and decreases the number of observable anodic redox waves by one when compared to complexes 2 and 3. Despite the decreasing electron density at the terminal or bridging alkenyl bipyridine ligand, the anodic redox processes still maintain appreciable ligand character as is seen by the shifts of the Ru(CO) and Re(CO)3 stretching frequencies on oxidation. Binding of the fac-Re(CO)3X moiety also attenuates the degree of ground-state delocalization in the mixed-valent states. We report here on ruthenium alkenyl complexes 2 and 3 derived from 2,2'-bipyridine and their Re(CO)3X adducts 4a,b and 5. Detailed electrochemical studies on these complexes and spectroscopic characterization of their oxidized forms by IR, UV/vis/NIR, and electron paramagnetic resonance spectroscopies as well as quantum chemical studies reveal sizable (bridging) ligand contributions to the redox orbitals. Engagement of the free bipy functions of complexes 2 and 3 in binding to the electron-withdrawing fac-Re(CO)3X (X = Br, Cl) moiety enhances the metal-to-ligand charge-transfer character of the optical excitations, causes sizable anodic shifts of the redox potentials, and decreases the number of observable anodic redox waves by one when compared to complexes 2 and 3. Despite the decreasing electron density at the terminal or bridging alkenyl bipyridine ligand, the anodic redox processes still maintain appreciable ligand character as is seen by the shifts of the Ru(CO) and Re(CO)3 stretching frequencies on oxidation. Binding of the fac-Re(CO)3X moiety also attenuates the degree of ground-state delocalization in the mixed-valent states.We report here on ruthenium alkenyl complexes 2 and 3 derived from 2,2'-bipyridine and their Re(CO)3X adducts 4a,b and 5. Detailed electrochemical studies on these complexes and spectroscopic characterization of their oxidized forms by IR, UV/vis/NIR, and electron paramagnetic resonance spectroscopies as well as quantum chemical studies reveal sizable (bridging) ligand contributions to the redox orbitals. Engagement of the free bipy functions of complexes 2 and 3 in binding to the electron-withdrawing fac-Re(CO)3X (X = Br, Cl) moiety enhances the metal-to-ligand charge-transfer character of the optical excitations, causes sizable anodic shifts of the redox potentials, and decreases the number of observable anodic redox waves by one when compared to complexes 2 and 3. Despite the decreasing electron density at the terminal or bridging alkenyl bipyridine ligand, the anodic redox processes still maintain appreciable ligand character as is seen by the shifts of the Ru(CO) and Re(CO)3 stretching frequencies on oxidation. Binding of the fac-Re(CO)3X moiety also attenuates the degree of ground-state delocalization in the mixed-valent states. |
| Author | Záliš, Stanislav Rotthowe, Nils He, Xiaoyan Abdel-Rahman, Obadah S Kvapilová, Hana Scheerer, Stefan Rigaut, Stéphane Winter, Rainer F |
| Author_xml | – sequence: 1 givenname: Stefan surname: Scheerer fullname: Scheerer, Stefan organization: †Fachbereich Chemie, Universität Konstanz, Universitätsstraße 10, D-78453 Konstanz, Germany – sequence: 2 givenname: Nils surname: Rotthowe fullname: Rotthowe, Nils organization: †Fachbereich Chemie, Universität Konstanz, Universitätsstraße 10, D-78453 Konstanz, Germany – sequence: 3 givenname: Obadah S surname: Abdel-Rahman fullname: Abdel-Rahman, Obadah S organization: †Fachbereich Chemie, Universität Konstanz, Universitätsstraße 10, D-78453 Konstanz, Germany – sequence: 4 givenname: Xiaoyan surname: He fullname: He, Xiaoyan organization: ‡Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, F-35042, Rennes Cedex, France – sequence: 5 givenname: Stéphane surname: Rigaut fullname: Rigaut, Stéphane organization: ‡Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, F-35042, Rennes Cedex, France – sequence: 6 givenname: Hana surname: Kvapilová fullname: Kvapilová, Hana organization: §J. Heyrovský Institute of Physical Chemistry, v.v.i., Academy of Sciences of the Czech Republic, Dolejškova 3, CZ-18223 Prague, Czech Republic – sequence: 7 givenname: Stanislav surname: Záliš fullname: Záliš, Stanislav organization: §J. Heyrovský Institute of Physical Chemistry, v.v.i., Academy of Sciences of the Czech Republic, Dolejškova 3, CZ-18223 Prague, Czech Republic – sequence: 8 givenname: Rainer F surname: Winter fullname: Winter, Rainer F organization: †Fachbereich Chemie, Universität Konstanz, Universitätsstraße 10, D-78453 Konstanz, Germany |
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| Title | Vinyl ruthenium-modified biphenyl and 2,2'-bipyridines |
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