title: Synthesis and reactivity of silylated tetrathiafulvalenes.
abstract: Novel organosilylated tetrathiafulvalenes (TTFs) possessing Si-H or Si-Si bonds have been synthesised. The crystal structures of several derivatives have been determined by X-ray diffraction, including that of dimeric (Si2Me4)(TTF)2 (11) incorporating a diatomic SiMe2-SiMe2 linker. Cyclic voltammetry measurements in all cases show two oxidation waves. DFT calculations were performed to rationalize the absence of an electronic communication between the two TTF moieties of 11 through the disilanyl spacer. The reactivity of the Si-H bond has been exploited to prepare the dinuclear complex [{Ru(CO)4}2{mu-(Me2Si)4TTF}] (14), starting from Ru3(CO)12 and TTF(SiMe2H)4 (1). Treatment of 14 with 2 equiv. of PPh3 or dppm results in selective substitution of a CO ligand trans to a SiMe2 group to afford mer-[{Ru(PPh3)(CO)3}2{mu-(Me2Si)4TTF}] (13) and mer-[{Ru(CO)3}2(eta1-dppm){mu-(Me2Si)4TTF}] (16). Attempts to transform the Si-H bonds of some TTF(SiMe2H)n (n = 1, 2) into Si-O functions using stoichiometric amounts of water in the presence of tris(dibenzylideneacetone)dipalladium(0) were unsuccessful. Quantitative cleavage of the C(TTF)-Si bond was observed instead of formation of TTF-based-siloxanes. Essays of catalytic bis-silylation of phenylacetylene with 11 and TTF(SiMe2-SiMe3) (9) in the presence of Pd(OAc)2/1,1,3,3-tetramethylbutylisocyanide failed. Again, cleavage of the C(TTF)-Si bond was noticed.
authors.affiliation: Institut UTINAM, UMR CNRS 6213, Université de Franche-Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030, Besançon, France.
authors.forename: Aurélien
authors.initials: A
authors.lastname: Hameau
authors.forename: Fabrice
authors.initials: F
authors.lastname: Guyon
authors.forename: Michael
authors.initials: M
authors.lastname: Knorr
authors.forename: Christian
authors.initials: C
authors.lastname: Däschlein
authors.forename: Carsten
authors.initials: C
authors.lastname: Strohmann
authors.forename: Narcis
authors.initials: N
authors.lastname: Avarvari