Reactivity of a Triruthenium Ynenyl Cluster Complex with Diynes: Cluster-Mediated Combination of up to Three Substituted Butadiyne Molecules into a Carbon-Rich Hydrocarbyl Ligand

Abstract

The triruthenium ynenyl cluster complex [Ru3(μ3-η2-apyr)(μ-η3-MeCH=CC≡CMe)(μ-CO)2(CO)6] (2; Hapyr = 2-aminopyrimidine) has been prepared in two steps from [Ru3(CO)12], 2-aminopyrimidine and 2,4-hexadiyne. Its reactivity with two conjugated diynes has been studied. With 2,4-hexadiyne, it affords [Ru3(μ3-η2-apyr){μ-η5-MeC≡CC=CMeC(=CHMe)C≡CMe}(μ-CO)2(CO)5] (3), which contains a diynedienyl ligand that arises from the coupling of 2,4-hexadiyne with the hex-2-yn-4-en-4-yl ligand of 2, whereas the reaction of complex 2 with diphenylbutadiyne gives [Ru3(μ3-η2-apyr){μ3-η7PhC≡CC=CPhCMe=CC(=CHMe)C(C≡CPh)=CPh}(μ-CO)(CO)6] (4). Complex 4 contains an unprecedented diynetetraentriyl ligand that arises from the coupling of two diphenylbutadiyne molecules with the hex-2-yn-4-en-4-yl ligand of 2. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)