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A Dibenzotetrathiafulvalene-Bridged Bis(alkenylruthenium) Complex and Its One- and Two-Electron-Oxidized Forms

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2023

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Inorganic Chemistry. ACS Publications. 2023, 62(46), S. 18789-18803. ISSN 0020-1669. eISSN 1520-510X. Verfügbar unter: doi: 10.1021/acs.inorgchem.3c03184

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We report on the synthesis of the new bis(alkenylruthenium) complex DBTTF-(ViRu)2 with a longitudinally extended, π-conjugated dibenzotetrathiafulvalene (DBTTF) bridge, characterized by multinuclear NMR, IR, and UV/vis spectroscopy, mass spectrometry, and single-crystal X-ray diffraction. Cyclic and square-wave voltammetry revealed that DBTTF-(ViRu)2 undergoes four consecutive oxidations. IR, UV/vis/near-IR, and electron paramagnetic resonance spectroscopy indicate that the first oxidation involves the redox-noninnocent DBTTF bridge, while the second oxidation is biased toward one of the peripheral styrylruthenium entities, thereby generating an electronically coupled mixed-valent state ({Ru}-CH═CH)•+-DBTTF•+-(CH═CH-{Ru}) [{Ru} = Ru(CO)Cl(PiPr3)2]. The latter is apparently in resonance with the ({Ru}-CH═CH)•+-DBTTF-(CH═CH-{Ru})•+ and ({Ru}-CH═CH)-DBTTF2+-(CH═CH-{Ru}) forms, which are calculated to lie within 19 kJ/mol. Higher oxidized forms proved too unstable for further characterization. The reaction of DBTTF-(ViRu)2 with the strong organic acceptors 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetracyano-p-benzoquinodimethane (TCNQ), and F4TCNQ resulted in formation of the DBTTF-(ViRu)2•+ radical cation, as shown by various spectroscopic techniques. Solid samples of these compounds were found to be highly amorphous and electrically insulating.

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Inorganic Chemistry

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ISO 690GOGESCH, Franciska S., Lukas LAININGER, Nick SOKOV, Stefan SCHUPP, Laura SENFT, Michael LINSEIS, Lukas SCHMIDT-MENDE, Miriam M. UNTERLASS, Rainer F. WINTER, 2023. A Dibenzotetrathiafulvalene-Bridged Bis(alkenylruthenium) Complex and Its One- and Two-Electron-Oxidized Forms. In: Inorganic Chemistry. ACS Publications. 2023, 62(46), S. 18789-18803. ISSN 0020-1669. eISSN 1520-510X. Verfügbar unter: doi: 10.1021/acs.inorgchem.3c03184
BibTex
@article{Gogesch2023-11-03Diben-68088,
  year={2023},
  doi={10.1021/acs.inorgchem.3c03184},
  title={A Dibenzotetrathiafulvalene-Bridged Bis(alkenylruthenium) Complex and Its One- and Two-Electron-Oxidized Forms},
  number={46},
  volume={62},
  issn={0020-1669},
  journal={Inorganic Chemistry},
  pages={18789--18803},
  author={Gogesch, Franciska S. and Laininger, Lukas and Sokov, Nick and Schupp, Stefan and Senft, Laura and Linseis, Michael and Schmidt-Mende, Lukas and Unterlass, Miriam M. and Winter, Rainer F.}
}
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    <dcterms:abstract>We report on the synthesis of the new bis(alkenylruthenium) complex DBTTF-(ViRu)&lt;sub&gt;2&lt;/sub&gt; with a longitudinally extended, π-conjugated dibenzotetrathiafulvalene (DBTTF) bridge, characterized by multinuclear NMR, IR, and UV/vis spectroscopy, mass spectrometry, and single-crystal X-ray diffraction. Cyclic and square-wave voltammetry revealed that DBTTF-(ViRu)&lt;sub&gt;2&lt;/sub&gt; undergoes four consecutive oxidations. IR, UV/vis/near-IR, and electron paramagnetic resonance spectroscopy indicate that the first oxidation involves the redox-noninnocent DBTTF bridge, while the second oxidation is biased toward one of the peripheral styrylruthenium entities, thereby generating an electronically coupled mixed-valent state ({Ru}-CH═CH)&lt;sup&gt;•+&lt;/sup&gt;-DBTTF&lt;sup&gt;•+&lt;/sup&gt;-(CH═CH-{Ru}) [{Ru} = Ru(CO)Cl(PiPr&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;]. The latter is apparently in resonance with the ({Ru}-CH═CH)•+-DBTTF-(CH═CH-{Ru})&lt;sup&gt;•+&lt;/sup&gt; and ({Ru}-CH═CH)-DBTTF&lt;sup&gt;2+&lt;/sup&gt;-(CH═CH-{Ru}) forms, which are calculated to lie within 19 kJ/mol. Higher oxidized forms proved too unstable for further characterization. The reaction of DBTTF-(ViRu)&lt;sub&gt;2&lt;/sub&gt; with the strong organic acceptors 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetracyano-p-benzoquinodimethane (TCNQ), and F&lt;sub&gt;4&lt;/sub&gt;TCNQ resulted in formation of the DBTTF-(ViRu)&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;•+&lt;/sup&gt; radical cation, as shown by various spectroscopic techniques. Solid samples of these compounds were found to be highly amorphous and electrically insulating.</dcterms:abstract>
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