Influence of the Temperature and Cation Nature on the EPR Spectra of Salts with the [Ni~(III)(η~5-1,2-B9C2H_(11))2]- Anion

摘要

The influence of specific features of the structure and nature of the cations (Ph4P~+, H(Phen)~+, Cs~+, and (CH3)4N~+) on the ERP spectra of the nickel ions in salts with the dicarbollylnickelate anion [Ni(B9C2H_(11))2]~- is studied. It is shown that the change in the cation type in these compounds results in the electron density redistribution, which affects the change in the main and average values of the g factor. The g_(av) value increases over that observed in frozen solutions upon the localization of the positive charge of the cation on one atom and in the absence of the screening effect of the solvent and large functional groups of the cation. The exception is the compound (Ph4P~+)NiCb2 (Cb is B9C2H_(11)) with solvated CCl4 molecules. For all compounds studied, the temperature dependence of the linewidths in the EPR spectra is described by the equation ΔH = αT + βT~7 with different α and β values and is defined by the temperature dependence of the relaxation process caused by the Raman interaction.