L?sungsmitteleinflu? auf das Redoxverhalten des Hexakismethylisonitrilmangan (I) ions |
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| Authors: | Gerhard Gritzner |
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| Institution: | (1) Leicester School of Pharmacy, De Montfort University, The Gateway, Leicester, LE1 9BH, UK;(2) Department of Chemistry, Faculty of Science, Sana’a University, P.O. Box 11923, Sana’a, Yemen;(3) Department of Chemistry, University at Buffalo, SUNY, Buffalo, NY 14260, USA; |
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| Abstract: | The redox behaviour of hexakismethylisonitrilmanganese(I) MnL
6
+] has been studied in acetic acid, dichloromethane, 1,2-dichloroethane, propylenecarbonate, butyrolactone, methanol, ethanol, nitromethane, acetonitrile, N-methyl-2-pyrrolidinone, dimethylformamide, dimethyl sulfoxide and water. The reversible diffusion-controlled oxidation MnL
6
+/MnL
6
2+ could be observed in all solvents studied, on both the dropping mercury electrode and the stationary platinum electrode. Employing tetrabutylammonium perchlorate as supporting electrolyte, the oxidation MnL
6
2+/MnL
6
3+ was observable only in acetic acid, nitromethane, 1,2-dichloroethane, dichloromethane, propylenecarbonate, butyrolactone and acetonitrile. In all other solvents oxidation of the solvent preceded the oxidation MnL
6
2+/MnL
6
3+. Poorly defined polarographic waves attributable to the one electron reduction of the MnL
6
+ were observed in butyrolactone, propylenecarbonate, acetonitrile, dimethylformamide, N-methyl-2-pyrrolidinone and dimethyl sulfoxide. All potential values were recorded versus bisbiphenylchromium(I)-iodide BBCr(I)J], the problems of measuring against external aqueous reference electrodes are discussed. The redox potential of the process MnL
6
+/MnL
6
2+ was found to be a function of the donor properties of the solvents used; the effects of outer sphere coordination on the redox behaviour of this couple are discussed. No effect of the supporting electrolytes tetrabutylammonium perchlorate, tetraethylammonium nitrate and tetraethylammonium perchlorate on the redox behaviour of MnL
6
+ was found. The UV-spectrum of MnL
6(PF6)2 has been recorded. |
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