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ansa-metallocene derivatives : XIV. Electrochemical reactions of unbridged and of tetramethylethanediyl-bridged chromocene carbonyl complexes

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1988

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Raaij, Edith U. van
Mönkeberg, Sigrid
Kiesele, Herbert

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http://nbn-resolving.de/urn:nbn:de:bsz:352-239752
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https://doi.org/10.1016/0022-328X(88)83148-6
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Journal of Organometallic Chemistry. 1988, 356(3), pp. 307-314. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(88)83148-6

Zusammenfassung

(C5H5)2Cr(CO), formed from chromocene and CO gas in THF solution at 0°C, loses its CO ligand upon one-electron oxidation. No CO loss is observed, on the other hand, when the ansa-chromocene carbonyl complex (CH3)4C2(C5H4)2Cr(CO) is oxidised to its monocation. Formation of a dication (CH3)4C2(C5H4)2Cr(CO)2+, for which there is no unbridged analogue, is irreversible owing to its fast conversion to a solvent adduct; its reduction under CO, however, quantitatively regenerates the neutral carbonyl complex. One-electron reduction of either of the carbonyl complexes, (C5H5)2Cr(CO) or (CH3)4C2(C5H4)2Cr(CO), induces a fast, irreversible decay of the chromocene framework.

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540 Chemie

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ISO 690RAAIJ, Edith U. van, Sigrid MÖNKEBERG, Herbert KIESELE, Hans-Herbert BRINTZINGER, 1988. ansa-metallocene derivatives : XIV. Electrochemical reactions of unbridged and of tetramethylethanediyl-bridged chromocene carbonyl complexes. In: Journal of Organometallic Chemistry. 1988, 356(3), pp. 307-314. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(88)83148-6
BibTex
@article{Raaij1988ansam-23975,
  year={1988},
  doi={10.1016/0022-328X(88)83148-6},
  title={ansa-metallocene derivatives : XIV. Electrochemical reactions of unbridged and of tetramethylethanediyl-bridged chromocene carbonyl complexes},
  number={3},
  volume={356},
  issn={0022-328X},
  journal={Journal of Organometallic Chemistry},
  pages={307--314},
  author={Raaij, Edith U. van and Mönkeberg, Sigrid and Kiesele, Herbert and Brintzinger, Hans-Herbert}
}
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    <dcterms:abstract xml:lang="eng">(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Cr(CO), formed from chromocene and CO gas in THF solution at 0°C, loses its CO ligand upon one-electron oxidation. No CO loss is observed, on the other hand, when the ansa-chromocene carbonyl complex (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Cr(CO) is oxidised to its monocation. Formation of a dication (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Cr(CO)&lt;sup&gt;2+&lt;/sup&gt;, for which there is no unbridged analogue, is irreversible owing to its fast conversion to a solvent adduct; its reduction under CO, however, quantitatively regenerates the neutral carbonyl complex. One-electron reduction of either of the carbonyl complexes, (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Cr(CO) or (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Cr(CO), induces a fast, irreversible decay of the chromocene framework.</dcterms:abstract>
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