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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

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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VAN 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

@article{van Raaij1988ansa--23980, title={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}, year={1988}, doi={10.1016/0022-328X(88)83149-8}, number={3}, volume={356}, issn={0022-328X}, journal={Journal of Organometallic Chemistry}, pages={315--323}, author={van Raaij, Edith U. and Brintzinger, Hans-Herbert} }

2013-08-13T09:03:37Z 1988 2013-08-13T09:03:37Z 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 Brintzinger, Hans-Herbert IR spectral data reveal that the 18-electron species (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Cr(CO) is reversibly transformed, at elevated CO pressures into a dicarbonyl complex, (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Cr(CO)<sub>2</sub>. Close coincidence of the v(CO) absorption bands of this dicarbonyl with those of (η<sup>3</sup>-C<sub>5</sub>H<sub>5</sub>)(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)W(CO)<sub>2</sub> and of η<sup>3</sup>-C<sub>5</sub>H<sub>7</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Cr(CO)<sub>2</sub> indicates that it contains an η<sup>3</sup>-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<sub>3</sub>)<sub>4</sub>C<sub>2</sub>-(C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>Cr(CO). The CO-induced transformation of this complex to (CH<sub>3</sub>)<sub>4</sub>C<sub>2</sub>(η<sup>3</sup>-C<sub>5</sub>H<sub>4</sub>)(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>)Cr(CO)<sub>2</sub> is greatly accelerated by small amounts of oxidants, i.e. by the formation of the cationic carbonyl complex (CH<sub>3</sub>)<sub>4</sub>C<sub>2</sub>(C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>Cr(CO)<sup>+</sup>, which appears to facilitate the CO-induced ring slippage by electron-transfer catalysis. deposit-license Brintzinger, Hans-Herbert van Raaij, Edith U. van Raaij, Edith U. Journal of Organometallic Chemistry ; 356 (1988), 3. - S. 315-323 eng

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