title: Tunable charge delocalization in dinickel quinonoid complexes.
abstract: When a 2,5-diamino-1,4-benzoquinonediimine C6H2(=NR)2(NHR)2 (2) is used as a bridging ligand, new dinickel(II) complexes [(acac)Ni[mu-C6H2(=NPh)4]Ni(acac)] (3a: R=Ph) and [(acac)Ni[mu-C6H2(=NCH2tBu)4]Ni(acac)] (3b: R=CH2tBu) are obtained; upon one-electron oxidation of these complexes delocalized mixed-valence compounds are formed. An X-ray diffraction study on 3b reveals equalization of the bond lengths within each of the ligand 6 systems and a lack of conjugation between them. The oxidized state in 3b+ involves both the bridging quinonoid ligand and the metal centers, with a major contribution coming from the bridging ligand. Electrochemical and spectroscopic methods were used to study the influence of the N-substituents of the tetranitrogen donor ligands 2. In this combined experimental and theoretical (DFT) study, it is also shown that the electronic structure within the dinickel system can be altered by addition of a coordinating ligand such as pyridine. The latter favors the high-spin configuration with semi-occupied metal-centered orbitals, leading to a metal-metal interaction in the mixed-valence Ni(II)-Ni(III) 3b+ system.
authors.affiliation: Laboratoire de Chimie de Coordination, UMR 7513 CNRS, Université Louis Pasteur, 4, rue Blaise Pascal, 67070 Strasbourg Cedex, France.
authors.forename: Olivier
authors.initials: O
authors.lastname: Siri
authors.forename: Jean-Philippe
authors.initials: JP
authors.lastname: Taquet
authors.forename: Jean-Paul
authors.initials: JP
authors.lastname: Collin
authors.forename: Marie-Madeleine
authors.initials: MM
authors.lastname: Rohmer
authors.forename: Marc
authors.initials: M
authors.lastname: Bénard
authors.forename: Pierre
authors.initials: P
authors.lastname: Braunstein