EPR Studies at High-Pressures. V. Spin-Exchange Reactions of Nitroxide Radicals with Cobalt and Nickel Complexes

Abstract

Abstract The rate constants kex for the spin exchange of nitroxides with various kinds of cobalt(II) and nickel(II) complexes were determined from the EPR line-broadening of nitroxides. The rate constants estimated were in the range of 108—109 M−1 s−1 and this reaction was found to be diffusion-controlled. In order to distinguish cases of strong and weak spin exchange, we examined the pressure dependence of the spin exchange between nitroxide and the complexes. It was found that the ligand in the first coordination sphere of the complexes plays an important role for the efficiency of spin exchange. The presence of the coordinated halide ion provides strong exchange, regardless of any screening of the complex’s internal atoms by organic molecules. From the pressure dependence of kex, the J2fs values (the exchange integral J and the steric factor fs) for the spin exchange of nitroxides with cobalt and nickel complexes were estimated to be about 1020 s−2. Based on the results, the steric hindrance for the reaction of spin exchange is discussed.