Titanocene-based group-11 metal ions; solid-state structure of {[(η5-C5H4SiMe3)2Ti(Ctriple bond; length of mdashCPh)2]2Ag}NO3

The reaction of [Ti](Ctriple bond; length of mdashCR)2 {[Ti] = (η5-C5H4SiMe3)2Ti; 1a, R = Fc, Fc = (η5-C5H4)Fe(η5-C5H5); 1b, R = Ph} with MX {2a, MX = [Cu(Ntriple bond; length of mdashCCH3)4]BF4; M = Ag; 2b, X = ClO4; 2c, X = NO3} in a 2:1 molar ratio produces the trinuclear heterobimetallic (Ti2M) or heptanuclear heterotrimetallic (Ti2MFe4) complexes [{[Ti](μ-σ,π-Ctriple bond; length of mdashCR)2}2M]X (R = Fc: 3a, M = Cu, X = BF4; 3b, M = Ag, X = ClO4. R = Ph: 3c, M = Cu, X = BF4; 3d, M = Ag, X = ClO4: 3e, M = Ag, X = NO3) in high yield. Complexes 3c–3e are also accessible, when {[Ti](μ-σ,π-Ctriple bond; length of mdashCPh)2}MX (M = Cu: 4a, X = FBF3; M = Ag: 4b, X = OClO3; 4c, X = ONO2) is reacted with one equivalent of 1b. Transferring this reaction scheme to [Ti](Ctriple bond; length of mdashCSiMe3)2 (1c) only the formation of the heterobimetallic tweezer complex {[Ti](μ-σ,π-Ctriple bond; length of mdashCSiMe3)2}MX {4d, MX = [Cu(Ntriple bond; length of mdashCCH3)]BF4; 4e, MX = AgOClO3} is observed which is attributed to the bulkiness of the acetylide-bound Me3Si group. The solid-state structure of 3e is reported. In 3e, two [Ti](Ctriple bond; length of mdashCPh)2 tweezer moieties are chelate-bound by their carbon–carbon triple bonds to a silver(I) ion, resulting in a pseudo-tetrahedral environment at the group-11 metal. View the MathML sourceNO3- is acting as counter-ion to cationic [{[Ti](Ctriple bond; length of mdashCPh)2}2Ag]+. Additionally, the result of cyclic voltammetric studies on [{[Ti](μ-σ,π-Ctriple bond; length of mdashCPh)2}2Cu]BF4 (3c) is reported.