Vinyl-ruthenium entities as markers for intramolecular electron transfer processes

The present account summarizes our work on mononuclear vinyl ruthenium complexes of the type RuCl(CHCHR′)(CO)(PR3)2L, divinyl-bridged diruthenium complexes {RuCl(CO)(PR3)2L}2(μ-CHCH-bridge-CHCH) 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(CHCH–) 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 CHCHR′ 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.

Subject (DDC)

540 Chemistry

Keywords

Ruthenium,Vinyl complexes,Electrochemistry,Spectroelectrochemistry,Mixed-valent

Cite This

ISO 690

MÜCKE, Philipp, Michael LINSEIS, Stanislav ZÁLIS, Rainer F. WINTER, 2011. Vinyl-ruthenium entities as markers for intramolecular electron transfer processes. In: Inorganica Chimica Acta. 374(1), pp. 36-50. ISSN 0020-1693. Available under: doi: 10.1016/j.ica.2011.03.071

BibTex

@article{Mucke2011Vinyl-13936,
  year={2011},
  doi={10.1016/j.ica.2011.03.071},
  title={Vinyl-ruthenium entities as markers for intramolecular electron transfer processes},
  number={1},
  volume={374},
  issn={0020-1693},
  journal={Inorganica Chimica Acta},
  pages={36--50},
  author={Mücke, Philipp and Linseis, Michael and Zális, Stanislav and Winter, Rainer F.}
}

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    <dcterms:abstract xml:lang="eng">The present account summarizes our work on mononuclear vinyl ruthenium complexes of the type RuCl(CHCHR′)(CO)(PR3)2L, divinyl-bridged diruthenium complexes {RuCl(CO)(PR3)2L}2(μ-CHCH-bridge-CHCH) 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(CHCH–) 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 CHCHR′ 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.</dcterms:abstract>
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Bibliography of Konstanz

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