Substitution of tetracyanoethene by ethynyl-metal complexes gives tricyanovinylethynyl (tricyanobutenynyl) derivatives: Syntheses, protonation, and addition of metal-ligand fragments

M.I. Bruce, M.A. Fox, Paul Low, B.K. Nicholson, C.R. Parker, W.C. Patalinghug, Brian Skelton, Allan White

Research output: Contribution to journalArticle

11 Citations (Scopus)


A series of complexes containing the new tricyanovinylethynyl (3,4,4-tricyanobut-3-en-1-ynyl) ligand have been obtained by substitution of a CN group in tetracyanoethene upon reaction with the ethynyl complexes M(C≡CH)(PP)Cp′ (M = Ru, Os, (PP)Cp′ = (PPh3)2Cp; M = Ru, PP = dppe, Cp′ = Cp, Cp*). The reactions proceed in higher yield as the metal environment becomes more sterically hindered, the normal [2 + 2]-cycloaddition/ring-opened product M{C[═C(CN)2]CH═C(CN)2}(PP)Cp′ also being formed in some cases. The diynyl complex Ru(C≡CC≡CH)(dppe)Cp* reacts with tcne to give only the ring-opened adduct Ru{C≡CC[═C(CN)2]CH═C(CN)2}(dppe)Cp*. Protonation (HBF4 or HPF6) of Ru{C≡CC(CN)═C(CN)2}(dppe)Cp* afforded the vinylidene cation [Ru{═C═CHC(CN)═C(CN)2}(dppe)Cp*]+. A second transition-metal fragment MLn (MLn = Ru(PPh3)2Cp, M′(dppe)Cp* (M′ = Ru, Os), RuCl(dppe)2) can be added to the CN group trans to the metal center; electrochemical, spectroscopic, and computational studies indicate that there is little ground-state delocalization between the metal centers. In the case of the tricyanovinylethynyl derivatives, an intense MLCT (or ML—LCT) transition can be identified in the visible region, which is responsible for the intense blue to purple color of these species; the analogous transition in the vinylidene-based complexes is significantly blue-shifted. The X-ray crystallographically determined structures of several of these complexes are reported. The cations [{Cp*(dppe)Ru}{μ-(C/N)≡CC(CN)═C(CN)(≡C/N)}{M(dppe)Cp*}]+ (M = Ru, Os) show some C≡C/C≡N disorder (and associated Ru/Os disorder in the case of the heterometallic example) in the crystals.
Original languageEnglish
Pages (from-to)2639-2657
Issue number7
Early online date1 Nov 2011
Publication statusPublished - 9 Apr 2012


Cite this