Maurer, Jorg and Sarkar, Bipraffit and Kaim, Wolfgang and Winter, Rainer F. and Zalis, Stanislav (2007) Towards new organometallic wires: Tetraruthenium complexes bridged by phenylenevinylene and vinylpyridine ligands. CHEMISTRY-A EUROPEAN JOURNAL, 13 (36). pp. 10257-10272. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
The tetranuclear complexes [{(PiPr(3))(2)(CO)ClRu(mu-CH=CHpy)Ru Cl(CO)(PPh3)(2)}(2)(mu-CH=CH-C6H4-CH=CH-1,4)] (3a) and [{(PiPr(3))(2)(CO)- ClRu(mu-CH=CHpy)RuCl(CO)(PPh3)(2)}(2)-(mu-CH=CH-C6H4-CH=CH-1,3)] (3b), which contain vinylpyridine ligands that connect peripheral Ru(PiPr(3))(2)(CO)Cl units to a central di-vinylphenylene-bridged diruthenium core, have been prepared and investigated. These complexes, in various oxidation states up to the tetracation level, have been characterized by standard electrochemical and spectroelectrochemical techniques, including IR, UV/Vis/NIR and ESR spectroscopy. A comparison with the results for the vinylpyridine-bridged dinuclear complex [PiPr(3))(2)(CO)ClRu(mu-CH=CHpy)RuCl-(CO)(PPh3)(2)(CH=CHPh)] (6) and the divinylphenylene-bridged complexes [{(EtOOCpy)(CO)Cl(PPh3)(2)Ru}(2)(mu- CH=CH-C6H4-CH=CH-1,4)] (8a) and [{(EtOOCpy)(CO)Cl(PPh3)(2)Ru}(2)(mu-CH=CH-C6H4-CH=CH-1,3)] (8 b), which represent the outer sections (6) or the inner core (8a,b) of complexes 3a,b, and with the mononuclear complex [(EtOOCpy)(CO)(PPh3)(2)RuCl(CH=CHPh)] (7) indicate that every accessible oxidation process is primarily centred on one of the vinyl ligands, with smaller contributions from the metal centres. The experimental results and quantum chemical calculations indicate charge- and spin-delocalization across the central divinylphenylenediruthenium part of 3a,b or the styrylruthenium unit of 6, but not beyond. The energy gap between the higher lying styryl- or divinylphenylenediruthenium-based and the lower occupied vinylpyridineruthenium-based orbitals increases in the order 6 < 3b < 3a and thus follows the conjugation within the non-heteroatom-substituted aromatic vinyl ligand.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ORDER REGULAR APPROXIMATION; INTRAMOLECULAR ELECTRON-TRANSFER; DENSITY-FUNCTIONAL CALCULATIONS; BIMETALLIC RUTHENIUM COMPLEXES; X-RAY STRUCTURE; MOLECULAR WIRES; DIRUTHENIUM COMPLEXES; RESONANCE RAMAN; VINYL LINKAGES; ABSORPTION; bridging ligands; conducting materials; density functional calculations; electrochemistry; ruthenium |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Alumni or Retired Professors > Arbeitskreis Prof. Dr. Rainer Winter |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 11 Jan 2021 11:28 |
| Last Modified: | 11 Jan 2021 11:28 |
| URI: | https://pred.uni-regensburg.de/id/eprint/33369 |
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