Magnetokinetic Effects in Reactions of Br2- and CH3• Radicals with Ni(Me2pyo[14]trieneN4)2+: Ligand Interchange-Imposed Restrictions on the Reactants Reencounter Probability

Magnetic field effects in reactions of CH3• and Br2- radicals with Ni(Me2pyo[14]trieneN4)2+ were investigated under magnetic inductions, B, between 0 and 7 T by flash photolysis. The dependences of the normalized rate constants, k(B)/k(0), on B do not conform to the model where the spin motion, Zeeman, and hyperfine and spin−orbit interactions are combined with free reencounters of radical-ion pairs. The experimental observations were better described when the dynamic-probability function was an exponential. The reasons for the observed magnetokinetic behavior in reactions of Ni(Me2pyo[14]trieneN4)2+, i.e., restrictions imposed by the dynamics of ligand interchange, are discussed.