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Reactive intermediates in the photolysis of cyclopentadienylcobalt(I) dicarbonyl and in the reduction of cyclopentadienylcobalt(III) carbonyl diiodide

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1977

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Lee, Wai-Sun

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http://nbn-resolving.de/urn:nbn:de:bsz:352-238660
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https://doi.org/10.1016/S0022-328X(00)84198-4
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Journal of Organometallic Chemistry. 1977, 127(1), pp. 87-92. ISSN 0022-328X. Available under: doi: 10.1016/S0022-328X(00)84198-4

Zusammenfassung

Photolysis of (C5H5)Co(CO)2(I) in toluene or petroleum ether solution at −78°C generates the unsaturated monocarbonyl species (C5H5)Co(CO), which was identified in solution by its IR spectrum. At room temperature, this monocarbonyl can associate with excess I to give (C5H5)2Co2(CO)3, or dimerize to (C5H5)2Co2(CO)2. The latter is stable as a solid, but in solution it is slowly converted to the insoluble trimer (C5H5)3Co3(CO)3. (C5H5)2Co2(CO)2 is symmetrically cleaved by phosphines to (C5H5)Co(CO)(PR3), while diolefins bring about unsymmetrical cleavage to give (C5H5)Co(diolefin) and (C5H5)Co(CO)2.

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540 Chemie

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ISO 690LEE, Wai-Sun, Hans-Herbert BRINTZINGER, 1977. Reactive intermediates in the photolysis of cyclopentadienylcobalt(I) dicarbonyl and in the reduction of cyclopentadienylcobalt(III) carbonyl diiodide. In: Journal of Organometallic Chemistry. 1977, 127(1), pp. 87-92. ISSN 0022-328X. Available under: doi: 10.1016/S0022-328X(00)84198-4
BibTex
@article{Lee1977React-23866,
  year={1977},
  doi={10.1016/S0022-328X(00)84198-4},
  title={Reactive intermediates in the photolysis of cyclopentadienylcobalt(I) dicarbonyl and in the reduction of cyclopentadienylcobalt(III) carbonyl diiodide},
  number={1},
  volume={127},
  issn={0022-328X},
  journal={Journal of Organometallic Chemistry},
  pages={87--92},
  author={Lee, Wai-Sun and Brintzinger, Hans-Herbert}
}
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    <dcterms:abstract xml:lang="eng">Photolysis of (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)Co(CO)&lt;sub&gt;2&lt;/sub&gt;(I) in toluene or petroleum ether solution at −78°C generates the unsaturated monocarbonyl species (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)Co(CO), which was identified in solution by its IR spectrum. At room temperature, this monocarbonyl can associate with excess I to give (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Co&lt;sub&gt;2&lt;/sub&gt;(CO)&lt;sub&gt;3&lt;/sub&gt;, or dimerize to (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Co&lt;sub&gt;2&lt;/sub&gt;(CO)&lt;sub&gt;2&lt;/sub&gt;. The latter is stable as a solid, but in solution it is slowly converted to the insoluble trimer (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt;Co&lt;sub&gt;3&lt;/sub&gt;(CO)&lt;sub&gt;3&lt;/sub&gt;. (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Co&lt;sub&gt;2&lt;/sub&gt;(CO)&lt;sub&gt;2&lt;/sub&gt; is symmetrically cleaved by phosphines to (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)Co(CO)(PR&lt;sub&gt;3&lt;/sub&gt;), while diolefins bring about unsymmetrical cleavage to give (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)Co(diolefin) and (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)Co(CO)&lt;sub&gt;2&lt;/sub&gt;.</dcterms:abstract>
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