793683-22-4Relevant academic research and scientific papers
Novel bonding modes between tetrathiafulvalenes (TTFS) and transition metal centers: π-bonding and covalent TTFSiMe2-MLn coordination to platinum
Jayaswal, Mathuresh N.,Peindy, Harmel N.,Guyon, Fabrice,Knorr, Michael,Avarvari, Narcis,Fourmigue, Marc
, p. 2646 - 2651 (2004)
Two novel strategies for coordinating TTF to transition metal centers have been developed. The reaction of tetrathiafulvalene (TTF) or 3,4- dimethyltetrathiafulvalene (o-Me2TTF) with [Pt(η2- C2H4)(PPh3)2] leads to the π complexes [Pt(η2-TTF)(PPh3)2] (1) and [Pt(η2-o-Me2TTF)(PPh3)2] (2), respectively. An X-ray crystallographic study performed on 2 confirmed, that TTFs act as a π acidic ligand. NMR studies revealed the existence, in solution, of an equilibrium between free and complexed TTF. Dilithiation of o-Me2TTF and subsequent silylation with ClSiMe2H afforded 3,4-dimethyl-3′,4′-(dimethylsilyl)tetrathiafulvalene (3), which has been structurally characterized. 3 reacts by oxidative addition across [Pt(η2-C2H4)(PPh3)2] to give [Pt{η2-o-(SiMe2)2-TTFMe 2}(PPh3)2] (4), in which the TTF ligand is covalently ligated to platinum via SiMe2 bridges. The redox properties of 3 and 4 have been investigated by cyclic voltammetry. Strong cathodic shifts of the two redox processes were observed for 4, implying the TTF core. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
