Article
Non-Innocence of 1,4-Dicyanamidobenzene Bridging Ligands in Dinuclear Ruthenium Complexes.
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† Chemistry Department, Carleton University, Ottawa, Ontario K1S 5B6, Canada
‡ Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, DE 70550 Stuttgart,Germany
§ Inorganic Chemistry, Freie Universitat Berlin, Fabeckstrasse 34-36, DE 14195 Berlin, Germany
Inorg. Chem., Article ASAP
DOI: 10.1021/ic401316g
Publication Date (Web): September 20, 2013
Copyright © 2013 American Chemical Society
*E-mail: robert_crutchley@carleton.ca.
Abstract
Four dinuclear complexes, [{RuII(ttpy)(bpy)}2(μ-L)][PF6]2, where bpy is 2,2′-bipyridine, ttpy is 4-(tert-butylphenyl)-2,2′:6′,2″-terpyridine, and L is 2,5-dimethyl-, 2,5-dichloro-, 2,3,4,5-tetrachloro- and unsubstituted 1,4-dicyanamidebenzene dianion have been synthesized and characterized. Electron paramagnetic resonance (EPR) spectroscopy of electrogenerated [{Ru(ttpy)(bpy)}2(μ-L)]3+ ions shows largely ligand centered spin and thus the complexes’ oxidation states are best formulated as [Ru(II), L•–, Ru(II)]3+. Visible-NIR and IR spectra of [{Ru(ttpy)(bpy)}2(μ-L)]3+,4+ ions were also obtained by spectroelectrochemical methods. For the [{Ru(ttpy)(bpy)}2(μ-L)]3+ ions, the significant variations in the spectra were rationalized in terms of an increased ruthenium contribution to the singly occupied molecular orbital with increasing number of chloro substituents on the bridging ligand L.
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