Variable-temperature and solvent NMR study of bis(μ2-methanethiolato)-bis(dinitrosyliron) and bis(μ2-methaneselenolato)-bis(dinitrosyliron) |
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| Authors: | Christopher Glidewell Andrew R. Hyde |
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| Affiliation: | Chemistry Department, University of St. Andrews, St. Andrews, Fife KY16 9ST, U.K. |
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| Abstract: | The 1H NMR spectrum of Fe2(SMe)2(NO)4 has been measured in a total of 22 solvents, and the activation barrier ΔG≠ for the C2h?C2v isomerisation in nine of these solvents. In aromatic solvents, the solvent-induced shifts are consistent with the formation of charge-transfer complexes, either 1:1 or 1:n; in non-aromatic, non-halogenated solvents of high dipolarity/polarizability the solvent-induced shifts follow the variation of the solvatochromic parameter, π*. The behaviour of Fe2(SeMe)2(NO)4 in a limited range of solvents is similar. The activation barrier ΔG≠ in Fe2(SMe)2(NO)4 is ca 78 kJ mol?1 in the majority of solvents, but that for Fe2(SeMe)2(NO)4 is significantly higher. |
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| Keywords: | Author to whom correspondence should be addressed. |
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