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ansa-metallocene derivatives : IX. Electrochemical reactions of tetramethylethylene-bridged titanocene dichloride and dicarbonyl derivatives

ansa-metallocene derivatives : IX. Electrochemical reactions of tetramethylethylene-bridged titanocene dichloride and dicarbonyl derivatives

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SCHWEMLEIN, Heinz, Wolfgang TRITSCHLER, Herbert KIESELE, Hans-Herbert BRINTZINGER, 1985. ansa-metallocene derivatives : IX. Electrochemical reactions of tetramethylethylene-bridged titanocene dichloride and dicarbonyl derivatives. In: Journal of Organometallic Chemistry. 293(3), pp. 353-364. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(85)80304-1

@article{Schwemlein1985ansam-23998, title={ansa-metallocene derivatives : IX. Electrochemical reactions of tetramethylethylene-bridged titanocene dichloride and dicarbonyl derivatives}, year={1985}, doi={10.1016/0022-328X(85)80304-1}, number={3}, volume={293}, issn={0022-328X}, journal={Journal of Organometallic Chemistry}, pages={353--364}, author={Schwemlein, Heinz and Tritschler, Wolfgang and Kiesele, Herbert and Brintzinger, Hans-Herbert} }

Kiesele, Herbert eng 1985 Brintzinger, Hans-Herbert deposit-license Tritschler, Wolfgang Brintzinger, Hans-Herbert In the reduction of tetramethylethylene-bridged (CH<sub>13</sub>)<sub>4</sub>C<sub>2</sub>(C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>TiCl<sub>2</sub> under argon, studied by cyclic voltammetry, a first reduction to the Ti<sup>III</sup> stage occurs at a potential of −0.92 V vs. SCE, close to that of (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>TiCl<sub>2</sub>, and a second reduction to the Ti<sup>II</sup> stage at a potential of −2.53 V, about 0.3 V more negative than in the corresponding reduction of the unbridged analogue. Decay of the tetramethylethylene-bridged Ti<sup>II</sup> product is considerably faster than that of its unbridged analogue. Changes induced by the presence of an N<sub>2</sub> or H<sub>2</sub> atmosphere indicate the occurrence of secondary reactions.<br /><br />In the presence of CO, reduction to (CH<sub>3</sub>)<sub>4</sub>C<sub>2</sub>(C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>Ti(CO)<sub>2</sub> occurs at −2.0 V. This tetramethylethylene-bridged titanocene dicarbonyl complex, which is also formed by reduction of (CH<sub>3</sub>)<sub>4</sub>C<sub>2</sub>(C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>TiCl<sub>2</sub> with Mg metal under CO, undergoes irreversible reduction and oxidation at −2.78 and −0.08 V, respectively. When the latter process is conducted in the presence of Cl<sup>−</sup>, the dichloride (CH<sub>3</sub>)<sub>4</sub>C<sub>2</sub>(C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>TiCl<sub>2</sub> is regenerated. Schwemlein, Heinz Kiesele, Herbert 2013-07-09T13:09:20Z 2013-07-09T13:09:20Z Tritschler, Wolfgang Schwemlein, Heinz Journal of Organometallic Chemistry ; 293 (1985), 3. - S. 353-364 ansa-metallocene derivatives : IX. Electrochemical reactions of tetramethylethylene-bridged titanocene dichloride and dicarbonyl derivatives

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