Abstract
Several paramagnetic tetrakis(diarylformamidinato)diruthenium(II,III) complexes bearing one phenylethynyl ligand at the axial position, Ru 2(ArNC(H)NAr) 4(CCPh) (Ar as p-ClC 6H 4 ( 2), m-ClC 6H 4 ( 3), m-CF 3C 6H 4 ( 4), 3,4-Cl 2C 6H 3 ( 5), and 3,5-Cl 2C 6H 3 ( 6)), were prepared and characterized. Cyclic voltammetry studies of 2– 6 revealed the presence of two one-electron redox couples: Ru 2 6+/Ru 2 5+ and Ru 2 5+/Ru 2 4+, and the half-wave potential for the latter correlates linearly with the Hammett constant ( σ) of the aryl substituent. Molecular structures of 3 and 6 were determined by X-ray crystallography. The nature of Ru 2–CC bonding interaction was predominantly Ru–C α σ-bonding based on the substituent-dependence of υ(CC), which decreases linearly with the increase of the Hammett constant σ of substituent.
Published Version
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