Electron-transfer induced change of direction of interannular haptotropic isomerization of fluorenyltricarbonylchromium anions |
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Authors: | S. V. Kukharenko L. N. Novikova V. V. Strelets N. A. Ustynyuk |
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Affiliation: | (1) Institute of Chemical Physics in Chemogolovka, Russian Academy of Sciences, 142432 Chemogolovka, Moscow Region, Russian Federation;(2) A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813 Moscow, Russian Federation |
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Abstract: | It has been shown by cyclic voltammetry in a THF medium in the temperature range from –70 °C to +20 °C that one-electron electrochemical reduction of (6-C13H10)Cr(CO)3 (1) to the corresponding 19-electron anion radical (1–) is accompanied by splitting off of a H atom to form the 18-electron carbon-centered anion (6-C13H9)Cr(CO)3 (–2), which at room temperature undergoes intramolecular haptotropic isomerization to the metal-centered (5-C13H9)Cr(CO)3– (–3) anion. The reversible one-electron reduction of3– to the corresponding 19-electron radical dianion32.– induces 5 6 interannular isomerization. In contrast to the equilibrium shift to the 5-isomer in 18-electron complexes 2 and 3, in their 19-electron analogs the equilibrium is shifted to the 6-isomer.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 48–53, January, 1994.This work was carried out with financial support from the Russian Foundation for Basic Research (no. 93-03-5209) |
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Keywords: | fluorenyltricarbonylchromium anion haptotropic rearrangement electrontransfer induced reactions cyclic voltammetry |
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