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The redox behavior of zerovalent palladium complexes of the types (i) Pd(N⌒N)(Q) (N⌒N = 2,2‘-bipyridine (bpy), 1,10-phenanthroline (phen), 1,4-dicyclohexyl-1,4-diaza-1,3-butadiene (chexDAB), bis(arylimino)acenaphthene (aryl = o,o-iPr2-C6H3; o,o-iPr2-BIAN), 2,2‘-bipyrimidine (bpym); Q = 1,4-benzoquinone (pbq), 1,4-naphthoquinone (nq), duroquinone (dq)) and (ii) Pd2(μ-N⌒N)(μ-pbq)2 (N⌒N = 4,5-diazafluorene (dafe), 4,5-diazafluoren-9-one (dafo)) was investigated by cyclic voltammetry and, in selected cases, by UV−vis spectroelectrochemistry and EPR spectroscopy. The character of the one-electron reduction of these complexes strongly depends on the π-acceptor properties of both types of redox-active ligands. The Q-localized reduction of Pd(N⌒N)(pbq) (N⌒N = chexDAB, phen, bpy) and Pd(bpy)(nq) leads to reversible dissociation of the p-semiquinone ligand, whereas the stable radical anion [Pd(bpym)(pbsq)]•- is produced on coordination of the stronger π-acceptor bpym ligand. The predominant localization of the elec...

Redox Properties of Zerovalent Palladium Complexes Containing α-Diimine andp-Quinone Ligands