Controlled Synthesis of Dinuclear Acetylide-Bridged Ruthenium Complexes
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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′ = tBu; R = Ph, R′ = tBu; R = tBu, R′ = 3,5-tBu2-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≡CC6H4C≡CH) at ambient temperature and pressure. These complexes were fully characterized by NMR spectroscopy, and trans,trans-(tBuC≡C)Ru(dmpe)2(μ-C≡CC6H4C≡C)Ru(dmpe)2(C≡CtBu) 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≡CC6H4C≡C)-Ru(dmpe)2(C≡CR) (R = Ph, tBu, SiMe3) were also prepared and characterized, and the redox behavior of a subset of the complexes was studied using cyclic voltammetry.
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