Ruthenium Complexes with Vinyl, Styryl, and Vinylpyrenyl Ligands: A Case of Non-innocence in Organometallic Chemistry

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2008
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Maurer, Jörg
Sarkar, Biprajit
Schwederski, Brigitte
Niemeyer, Mark
Kaim, Wolfgang
Zális, Stanislav
Anson, Chris
Zabel, Manfred
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Journal of the American Chemical Society ; 130 (2008), 1. - pp. 259-268. - ISSN 0002-7863. - eISSN 1520-5126
Abstract
We herein describe a systematic account of mononuclear ruthenium vinyl complexes L−{Ru}−CHCH−R where the phosphine ligands at the (PR‘3)2Ru(CO)Cl{Ru} moiety, the coordination number at the metal (L = 4-ethylisonicotinate or a vacant coordination site) and the substituent R (R = nbutyl, phenyl, 1-pyrenyl) have been varied. Structures of the enynyl complex Ru(CO)Cl(PPh3)2(η1:η2-nBuHCCHCCnBu), which results from the coupling of the hexenyl ligand of complex 1a with another molecule of 1-hexyne, of the hexenyl complexes (nBuCHCH)Ru(CO)Cl(PiPr3)2 (1c) and (nBuCHCH)Ru(CO)Cl(PPh3)2(NC5H4COOEt-4) (1b), and of the pyrenyl complexes (1-Pyr-CHCH)Ru(CO)Cl(PiPr3)2 (3c) and (1-Pyr-CHCH)Ru(CO)Cl(PPh3)3 (3a-P) have been established by X-ray crystallography. All vinyl complexes undergo a one-electron oxidation at fairly low potentials and a second oxidation at more positive potentials. Anodic half-wave or peak potentials show a progressive shift to lower values as π-conjugation within the vinyl ligand increases. Carbonyl band shifts of the metal-bonded CO ligand upon monooxidation are significantly smaller than is expected of a metal-centered oxidation process and are further diminished as the vinyl CHCH entity is incorporated into a more extended π-system. ESR spectra of the electrogenerated radical cations display negligible g-value anisotropies and small deviations of the average g-value from that of the free electron. The vinyl ligands thus strongly contribute to or even dominate the anodic oxidation processes. This renders them a class of truly “non-innocent” ligands in organometallic ruthenium chemistry. Experimental findings are fully supported by quantum chemical calculations: The contribution of the vinyl ligand to the HOMO increases from 46% (Ru-vinyl delocalized) to 84% (vinyl dominated) as R changes from nbutyl to 1-pyrenyl.
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ISO 690MAURER, Jörg, Michael LINSEIS, Biprajit SARKAR, Brigitte SCHWEDERSKI, Mark NIEMEYER, Wolfgang KAIM, Stanislav ZÁLIS, Chris ANSON, Manfred ZABEL, Rainer F. WINTER, 2008. Ruthenium Complexes with Vinyl, Styryl, and Vinylpyrenyl Ligands: A Case of Non-innocence in Organometallic Chemistry. In: Journal of the American Chemical Society. 130(1), pp. 259-268. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja075547t
BibTex
@article{Maurer2008-01-09Ruthe-13826,
  year={2008},
  doi={10.1021/ja075547t},
  title={Ruthenium Complexes with Vinyl, Styryl, and Vinylpyrenyl Ligands: A Case of Non-innocence in Organometallic Chemistry},
  number={1},
  volume={130},
  issn={0002-7863},
  journal={Journal of the American Chemical Society},
  pages={259--268},
  author={Maurer, Jörg and Linseis, Michael and Sarkar, Biprajit and Schwederski, Brigitte and Niemeyer, Mark and Kaim, Wolfgang and Zális, Stanislav and Anson, Chris and Zabel, Manfred and Winter, Rainer F.}
}
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    <dcterms:abstract xml:lang="eng">We herein describe a systematic account of mononuclear ruthenium vinyl complexes L−{Ru}−CHCH−R where the phosphine ligands at the (PR‘3)2Ru(CO)Cl{Ru} moiety, the coordination number at the metal (L = 4-ethylisonicotinate or a vacant coordination site) and the substituent R (R = nbutyl, phenyl, 1-pyrenyl) have been varied. Structures of the enynyl complex Ru(CO)Cl(PPh3)2(η1:η2-nBuHCCHCCnBu), which results from the coupling of the hexenyl ligand of complex 1a with another molecule of 1-hexyne, of the hexenyl complexes (nBuCHCH)Ru(CO)Cl(PiPr3)2 (1c) and (nBuCHCH)Ru(CO)Cl(PPh3)2(NC5H4COOEt-4) (1b), and of the pyrenyl complexes (1-Pyr-CHCH)Ru(CO)Cl(PiPr3)2 (3c) and (1-Pyr-CHCH)Ru(CO)Cl(PPh3)3 (3a-P) have been established by X-ray crystallography. All vinyl complexes undergo a one-electron oxidation at fairly low potentials and a second oxidation at more positive potentials. Anodic half-wave or peak potentials show a progressive shift to lower values as π-conjugation within the vinyl ligand increases. Carbonyl band shifts of the metal-bonded CO ligand upon monooxidation are significantly smaller than is expected of a metal-centered oxidation process and are further diminished as the vinyl CHCH entity is incorporated into a more extended π-system. ESR spectra of the electrogenerated radical cations display negligible g-value anisotropies and small deviations of the average g-value from that of the free electron. The vinyl ligands thus strongly contribute to or even dominate the anodic oxidation processes. This renders them a class of truly “non-innocent” ligands in organometallic ruthenium chemistry. Experimental findings are fully supported by quantum chemical calculations: The contribution of the vinyl ligand to the HOMO increases from 46% (Ru-vinyl delocalized) to 84% (vinyl dominated) as R changes from nbutyl to 1-pyrenyl.</dcterms:abstract>
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