ansa-metallocene derivatives : XV. Reversible coordination of a second CO ligand to (C5H5)2Cr(CO) and its tetramethylethanediyl-bridged analogue. Evidence for an electron-transfer catalysed ring-slippage reaction. IR studies at elevated gas pressure. II

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1988
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van Raaij, Edith U.
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Journal of Organometallic Chemistry ; 356 (1988), 3. - pp. 315-323. - ISSN 0022-328X. - eISSN 1872-8561
Abstract
IR spectral data reveal that the 18-electron species (C5H5)2Cr(CO) is reversibly transformed, at elevated CO pressures into a dicarbonyl complex, (C5H5)2Cr(CO)2. Close coincidence of the v(CO) absorption bands of this dicarbonyl with those of (η3-C5H5)(η5-C5H5)W(CO)2 and of η3-C5H75-C5H5)Cr(CO)2 indicates that it contains an η3-bound ring ligand. Equlibrium and kinetic data have been obtained for this CO-induced ring-slippage reaction and for an analogous reaction involving the tetramethylethanediyl-bridged ansa-chromocene carbonyl complex (CH3)4C2-(C5H4)2Cr(CO). The CO-induced transformation of this complex to (CH3)4C23-C5H4)(η5-C5H4)Cr(CO)2 is greatly accelerated by small amounts of oxidants, i.e. by the formation of the cationic carbonyl complex (CH3)4C2(C5H4)2Cr(CO)+, which appears to facilitate the CO-induced ring slippage by electron-transfer catalysis.
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ISO 690VAN RAAIJ, Edith U., Hans-Herbert BRINTZINGER, 1988. ansa-metallocene derivatives : XV. Reversible coordination of a second CO ligand to (C5H5)2Cr(CO) and its tetramethylethanediyl-bridged analogue. Evidence for an electron-transfer catalysed ring-slippage reaction. IR studies at elevated gas pressure. II. In: Journal of Organometallic Chemistry. 356(3), pp. 315-323. ISSN 0022-328X. eISSN 1872-8561. Available under: doi: 10.1016/0022-328X(88)83149-8
BibTex
@article{vanRaaij1988ansam-23980,
  year={1988},
  doi={10.1016/0022-328X(88)83149-8},
  title={ansa-metallocene derivatives : XV. Reversible coordination of a second CO ligand to (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Cr(CO) and its tetramethylethanediyl-bridged analogue. Evidence for an electron-transfer catalysed ring-slippage reaction. IR studies at elevated gas pressure. II},
  number={3},
  volume={356},
  issn={0022-328X},
  journal={Journal of Organometallic Chemistry},
  pages={315--323},
  author={van Raaij, Edith U. and Brintzinger, Hans-Herbert}
}
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    <dcterms:title>ansa-metallocene derivatives : XV. Reversible coordination of a second CO ligand to (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) and its tetramethylethanediyl-bridged analogue. Evidence for an electron-transfer catalysed ring-slippage reaction. IR studies at elevated gas pressure. II</dcterms:title>
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    <dcterms:abstract xml:lang="eng">IR spectral data reveal that the 18-electron species (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) is reversibly transformed, at elevated CO pressures into a dicarbonyl complex, (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)&lt;sub&gt;2&lt;/sub&gt;. Close coincidence of the v(CO) absorption bands of this dicarbonyl with those of (η&lt;sup&gt;3&lt;/sup&gt;-C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)(η&lt;sup&gt;5&lt;/sup&gt;-C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)W(CO)&lt;sub&gt;2&lt;/sub&gt; and of η&lt;sup&gt;3&lt;/sup&gt;-C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;7&lt;/sub&gt;(η&lt;sup&gt;5&lt;/sup&gt;-C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)Cr(CO)&lt;sub&gt;2&lt;/sub&gt; indicates that it contains an η&lt;sup&gt;3&lt;/sup&gt;-bound ring ligand. Equlibrium and kinetic data have been obtained for this CO-induced ring-slippage reaction and for an analogous reaction involving the tetramethylethanediyl-bridged 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). The CO-induced transformation of this complex to (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(η&lt;sup&gt;3&lt;/sup&gt;-C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)(η&lt;sup&gt;5&lt;/sup&gt;-C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)Cr(CO)&lt;sub&gt;2&lt;/sub&gt; is greatly accelerated by small amounts of oxidants, i.e. by the formation of the cationic 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)&lt;sup&gt;+&lt;/sup&gt;, which appears to facilitate the CO-induced ring slippage by electron-transfer catalysis.</dcterms:abstract>
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