Redox reactions of the boron subhalide clusters BnCln0/˙−/2− (n = 8 or 9) investigated by electrochemical and spectroscopic methods †
| Autor: | Bernd Speiser, Ronald Schäfer, Carsten Tittel, Wolfgang Einholz |
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| Rok vydání: | 1999 |
| Předmět: | |
| Zdroj: | Journal of the Chemical Society, Dalton Transactions. :1741-1752 |
| ISSN: | 1364-5447 0300-9246 |
| DOI: | 10.1039/a809134j |
| Popis: | The redox properties of the electron hyperdeficient boron subhalide clusters octachlorooctaborane(8), B8Cl8, and nonachlorononaborane(9), B9Cl9, were investigated in solution by cyclic voltammetry at platinum or glassy carbon electrodes, and by 11B NMR as well as ESR spectroscopy. The neutral compounds undergo a spontaneous reduction by traces of moisture usually present even in dried solvents, and the voltammetric experiment starts from B8Cl8˙– or B9Cl9˙–. The radical anions were identified by ESR spectroscopy. Their formation leads to line broadening in NMR spectra of BnCln. Electrochemically, they are quasireversibly reduced to the dianions, but oxidized in an ECcat (electrochemical step, catalytic chemical step) reaction with an essentially reversible electron transfer step to the neutral compounds. The potential ordering for the two redox processes is “normal” in both clusters, being in accordance with the fact that structural changes accompanying the electron transfer are minor. The radical anion B8Cl8˙– is even more stable against disproportionation than B9Cl9˙–. |
| Databáze: | OpenAIRE |
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