title: Metal-Induced Thiophene Ring Opening and C-C Bond Formation To Produce Unique Hexa-1,3,5-trienediyl-Coupled Non-Innocent Ligand Chelates.
abstract: Ring opening of thiophenes containing an azo function in 2-position and subsequent dimerization through C-C coupling were observed on reaction with [Ru(acac)2 (CH3 CN)2 ] (acac=acetylacetonate) to produce two 1,3,5-hexatriene-linked redox-active azothiocarbonyl chelate systems. Interaction of the non-innocent chelate ligands and of the metals at a nanoscale distance of 1.45 nm via the conjugated hexatriene bridge was studied by magnetic and electron spectroscopic measurements in conjunction with DFT calculations, revealing four-center magnetic interactions of this unique setting and weak intervalence coupling after reduction.
authors.affiliation: Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70550 Stuttgart (Germany).
authors.forename: Fabian
authors.initials: F
authors.lastname: Ehret
authors.affiliation: Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70550 Stuttgart (Germany).
authors.forename: Martina
authors.initials: M
authors.lastname: Bubrin
authors.affiliation: J. Heyrovský Institute of Physical Chemistry, v.v.i., Academy of Sciences of the Czech Republic, Dolejškova 3, 18223 Prague (Czech Republic).
authors.forename: Stanislav
authors.initials: S
authors.lastname: Záliš
authors.affiliation: Facultad de Ciencias Químicas, Universidad, Complutense de Madrid, 28040 Madrid (Spain).
authors.forename: José Luis
authors.initials: JL
authors.lastname: Priego
authors.affiliation: Facultad de Ciencias Químicas, Universidad, Complutense de Madrid, 28040 Madrid (Spain).
authors.forename: Reyes
authors.initials: R
authors.lastname: Jiménez-Aparicio
authors.affiliation: Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70550 Stuttgart (Germany). kaim@iac.uni-stuttgart.de.
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Kaim
keywords: mixed valence; non-innocent ligand; ruthenium; spin coupling; thiophene