Some chemistry of trans-Ru(CCCCH)2(dppe)2: Syntheses of bi- and tri-metallic derivatives and cycloaddition of tcne

Conventional reactions of trans-Ru(CCCCH)2(dppe)21 with RuCl(PP)Cp′ or AuCl(PPh3) have given the complexes trans-Ru(CCCCR)(CCCCR′)(dppe)2 [R = H, Ru(PP)Cp′, Au(PPh3); R′ = Ru(PP)Cp′, (PP)Cp′ = (PPh3)2Cp, (dppe)Cp, (dppe)Cp∗ (not all combinations)]. The Au(PPh3) derivatives react with Co(μ3-CBr)(μ-dppm)(CO)7 to give trans-Ru(CCCCH){CCCCC[Co3(μ-dppm)(CO)7]}(dppe)2 and trans-Ru{CCCCC[Co3(μ-dppm)(CO)7]}2(dppe)2, which contain respectively four- and five-carbon and two five-carbon chains linking the metal centres. Also described is the addition of tcne to trans-Ru(CCCCH)2(dppe)2 to give the bis(η1-tetracyanobutadienyl) complex trans-Ru{CCC[C(CN)2]CHC(CN)2}2(dppe)211, of which the single crystal X-ray structure is reported.

Graphical abstractReactions of trans-Ru(CCCCH)2(dppe)21 with RuCl(PP)Cp’ or AuCl(PPh3) have given the complexes trans-Ru(CCCCR)(CCCCR’)(dppe)2 [R = H, Ru(PP)Cp’, Au(PPh3); R’ = Ru(PP)Cp’, (PP)Cp’ = (PPh3)2Cp, (dppe)Cp, (dppe)Cp∗ (not all combinations)]; the Au(PPh3) derivatives react with Co(μ3-CBr)(μ-dppm)(CO)7 to give trans-Ru(CCCCH){CCCCC[Co3(μ-dppm)(CO)7]}(dppe)2 and trans-Ru{CCCCC[Co3(μ-dppm)(CO)7]}(dppe)2. Addition of tcne to trans-Ru(CCCCH)2(dppe)2 gives trans-Ru{CCC[C(CN)2]CHC(CN)2}2(dppe)2.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Synthesis of a bis(diynyl)ruthenium–phosphine complex. ► Reactions with Ru or Au reagents to give di- and tri-metallic derivatives. ► Au complexes give Co3 cluster compounds with C4 + C5 or 2 × C5 chains. ► Synthesis, structure of ring-opened adduct of tcne with Ru(diynyl) complex.