Controlled synthesis of dinuclear acetylide-bridged ruthenium complexes

Abstract

A series of dinuclear and trinuclear, acetylide-bridged ruthenium(II) complexes was synthesized by the condensation of terminal acetylenes with methyl ruthenium complexes. Dinuclear ruthenium(II) complexes trans,trans-(RC=C) Ru(dmpe)2(µ-C=CC6H4C=C)Ru(C=CR')(dmpe) 2 (R = R' = Ph; R = R/ = 'Bu; R = Ph, R' = 'Bu; R = 'Bu, R' = 3,5-'Bu2-C6H3) were synthesized by the reaction of trans-(CH3)Ru(dmpe)2(C=CR) with the unsymmetrical bis(acetylido)ruthenium(II) complex trans-(R'C=C)Ru(dmpe)2(C=CC 6H4C=CH) at ambient temperature and pressure. These complexes were fully characterized by NMR spectroscopy, and trans,trans-('BuC=C) Ru(dmpe)2(µ-C=CC6H4C=C)Ru(dmpe) 2(C=C'Bu) was characterized crystallographically. The symmetrical trinuclear ruthenium(II) complexes trans,trans,trans-(RC=C)Ru(dmpe) 2(µ-C=CC6H4C=C)Ru(depe)2(µ-C=CC 6H4C=C)-Ru(dmpe)2(C=CR) (R = Ph, 'Bu, SiMe 3) were also prepared and characterized, and the redox behavior of a subset of the complexes was studied using cyclic voltammetry. © 2010 American Chemical Society.</p