SOLVENT CONTROL OF ORBITAL MIXING AND ELECTRONIC COUPLING IN LIGAND-BRIDGED MIXED-VALENCE COMPLEXES - EVIDENCE FOR AN INTERVALENCE HOLE-TRANSFER PATHWAY

Solvent-induced electronic effects exist for intervalence charge-transfer reactions involving complexes of the type (2,2'-bipyridine)2ClRuII(pyrazine)RuIII(NH3)4L4+, where L = NH3 or various pyrazyl, pyridyl, or polypyridyl ligands. Specifically the following are found: (1) Mixing between appropriate donor and acceptor metal orbitals can be influenced substantially by the nature of the solvent. (2) The metal-metal interaction energy, H13, is also affected. (3) From the solvent effects, intervalence transfer appears to follow (in part) a hole-transfer pathway. © 1990, American Chemical Society. All rights reserved.