Vinyl-ruthenium entities as markers for intramolecular electron transfer processes |
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Authors: | Philipp Mücke [Author Vitae] [Author Vitae] Stanislav Záliš [Author Vitae] [Author Vitae] |
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Institution: | a Institut für Anorganische Chemie, Universität Konstanz, Universitätsstraße 10, D-78453 Konstanz, Germany b J. Heyrovský Institute of Physical Chemistry, v.v.i, Academy of Sciences of the Czech Republic, Dolejškova 3, 182 23 Prague, Czech Republic |
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Abstract: | The present account summarizes our work on mononuclear vinyl ruthenium complexes of the type RuCl(CH CHR′)(CO)(PR3)2L, divinyl-bridged diruthenium complexes {RuCl(CO)(PR3)2L}2(μ-CH CH-bridge-CH CH) and on heterobinuclear systems where only one of the two redox-active metal-organic moieties is of the vinyl ruthenium type. The favourable electrochemical properties of the {RuCl(CO)(PR3)2L(CH CH-) tag and the various spectroscopic handles offered by that unit provide detailed insights into the charge and spin delocalization over the {MCl(CO)(PR3)2L} and CH CHR′ constituents in their associated radical cations. They also offer a convenient means for measuring electronic coupling in the mixed-valent radical cations of the homo- and heterodinuclear vinyl-bridged complexes and, under favourable circumstances, on the rate of intramolecular electron transfer between the individual redox sites. Aspects of this work include examples of complexes showing time-dependent valence trapping, complexes aimed at delineating the efficiencies of through-space versus through-bond pathways for electron delocalization, complexes where electrostatic effects on the redox splitting ΔE1/2 dominate over those from the resonance contribution and systems that exhibit extensive charge and spin delocalization between two dislike endgroups despite their intrinsically different redox potentials. |
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Keywords: | Ruthenium Vinyl complexes Electrochemistry Spectroelectrochemistry Mixed-valent |
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