Comparison of electron-transfer matrix elements for transition-metal complexes: t2g vs. eg transfer and ammine vs. aqua ligands

摘要: Electron-transfer matrix elements are calculated for several pairs of transition-metal complexes the type ML/sub 6//sup 2 +/-ML/sub 3 +/, chosen so as to allow a comparison t/sub 2g/(..pi..) vs. e/sub g/(sigma) transfer and NH/sub 3/ H/sub 2/O ligands, primarily apex-to-apex orientation reactants (M = Fe, Co, Ru). The magnitude element has pronounced dependence on (e/sub g/ > 2g/) ligand (NH/sub 2/O), an effect which is correlated with degree mixing metal orbitals, based corresponding orbital analysis. Use Co(NH/sub 3/)/sub 2+/3+/ electron exchange, in conjunction semiclassical kinetic formalism spin-orbit attenuation factor, yields rate constant ground-state reaction path about orders less than experimental constant. (Orientational averaging would lower even further.)