Fully Delocalized (Ethynyl)(vinyl)phenylene Bridged Triruthenium Complexes in up to Five Different Oxidation States

Wuttke, Evelyn; Pevny, Florian; Hervault, Yves-Marie; Norel, Lucie; Drescher, Malte; Winter, Rainer F.; Rigaut, Stephane

Fully Delocalized (Ethynyl)(vinyl)phenylene Bridged Triruthenium Complexes in up to Five Different Oxidation States

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Datum

2012

Autor:innen

Wuttke, Evelyn

Pevny, Florian

Hervault, Yves-Marie

Norel, Lucie

Drescher, Malte

Winter, Rainer F.

Rigaut, Stephane

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Zeitschriftenartikel

Publikationsstatus

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Inorganic Chemistry. 2012, 51(3), pp. 1902-1915. ISSN 0020-1669. eISSN 1520-510X. Available under: doi: 10.1021/ic2022177

Zusammenfassung

Triruthenium (dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)}(2) (4a, R = H; 4b, R = OMe) containing unsymmetrical (ethynyl)(vinyl)phenylene bridging ligands and displaying five well-separated redox states (n = 0-4) are compared to their bis(alkynyl)ruthenium precursors (dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡CR'} (2a,b: R' = TMS; 3a,b: R' = H) and their symmetrically substituted bimetallic congeners, complexes {Cl(dppe)(2)Ru}(2){μ-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡C} (A(a), R = H; A(b), R = OMe) and {RuCl(CO)(P(i)Pr(3))(2)}(2){μ-CH═CH-1,4-C(6)H(2)-2,5-R(2)-CH═CH} (V(a), R = H; V(b), R = OMe) as well as the mixed (ethynyl)(vinyl)phenylene bridged [Cl(dppe)(2)Ru-C≡C-1,4-C(6)H(4)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)] (M(a)). Successive one-electron transfer steps were studied by means of cyclic voltammetry, EPR and UV-vis-NIR-IR spectroelectrochemistry. These studies show that the first oxidation mainly involves the central bis(alkynyl) ruthenium moiety with only limited effects on the appended vinyl ruthenium moieties. The second to fourth oxidations (n = 2, 3, 4) involve the entire carbon-rich conjugated path of the molecule with an increased charge uniformly distributed between the two arms of the molecules, including the terminal vinyl ruthenium sites. In order to assess the charge distribution, we judiciously use (13)CO labeled analogues to distinguish stretching vibrations due to the acetylide triple bonds and the intense and charge-sensitive Ru(CO) IR probe in different oxidation states. The comparison between complex pairs 4a,b(n+) (n = 0-3), A(a,b)(n+) and V(a,b)(n+) (n = 0-2) serves to elucidate the effect of the methoxy donor substituents on the redox and spectroscopic properties of these systems in their various oxidation states and on the metal/ligand contributions to their frontier orbitals.

Fachgebiet (DDC)

540 Chemie

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ISO 690

WUTTKE, Evelyn, Florian PEVNY, Yves-Marie HERVAULT, Lucie NOREL, Malte DRESCHER, Rainer F. WINTER, Stephane RIGAUT, 2012. Fully Delocalized (Ethynyl)(vinyl)phenylene Bridged Triruthenium Complexes in up to Five Different Oxidation States. In: Inorganic Chemistry. 2012, 51(3), pp. 1902-1915. ISSN 0020-1669. eISSN 1520-510X. Available under: doi: 10.1021/ic2022177

BibTex

@article{Wuttke2012-02-06Fully-20627,
  year={2012},
  doi={10.1021/ic2022177},
  title={Fully Delocalized (Ethynyl)(vinyl)phenylene Bridged Triruthenium Complexes in up to Five Different Oxidation States},
  number={3},
  volume={51},
  issn={0020-1669},
  journal={Inorganic Chemistry},
  pages={1902--1915},
  author={Wuttke, Evelyn and Pevny, Florian and Hervault, Yves-Marie and Norel, Lucie and Drescher, Malte and Winter, Rainer F. and Rigaut, Stephane}
}

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