Non-Innocence of 1,4-Dicyanamidobenzene Bridging Ligands in Dinuclear Ruthenium Complexes

Autor:	Robert J. Crutchley, Wolfgang Kaim, Biprajit Sarkar, Mohommad M. R. Choudhuri
Rok vydání:	2013
Předmět:	Chemistry Ligand chemistry.chemical_element Infrared spectroscopy Bridging ligand Ruthenium Ion law.invention Inorganic Chemistry Crystallography law Molecular orbital Physical and Theoretical Chemistry Electron paramagnetic resonance Spectroscopy
Zdroj:	Inorganic Chemistry. 52:11060-11066
ISSN:	1520-510X 0020-1669
DOI:	10.1021/ic401316g
Popis:	Four dinuclear complexes, [{Ru(II)(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.
Databáze:	OpenAIRE
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