Novel Bonding Modes between Tetrathiafulvalenes (TTFs) and Transition Metal Centers: π-Bonding and Covalent TTFSiMe2−MLn Coordination to Platinum
✍ Scribed by Mathuresh N. Jayaswal; Harmel N. Peindy; Fabrice Guyon; Michael Knorr; Narcis Avarvari; Marc Fourmigué
- Publisher
- John Wiley and Sons
- Year
- 2004
- Tongue
- English
- Weight
- 166 KB
- Volume
- 2004
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
Abstract
Two novel strategies for coordinating TTF to transition metal centers have been developed. The reaction of tetrathiafulvalene (TTF) or 3,4‐dimethyltetrathiafulvalene (o‐Me~2~TTF) with [Pt(η^2^‐C~2~H~4~)(PPh~3~)~2~] leads to the π complexes [Pt(η^2^‐TTF)(PPh~3~)~2~] (1) and [Pt(η^2^‐o‐Me~2~TTF)(PPh~3~)~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‐Me~2~TTF and subsequent silylation with ClSiMe~2~H afforded 3,4‐dimethyl‐3′,4′‐(dimethylsilyl)tetrathiafulvalene (3), which has been structurally characterized. 3 reacts by oxidative addition across [Pt(η^2^‐C~2~H~4~)(PPh~3~)~2~] to give [Pt{η^2^‐o‐(SiMe~2~)~2~TTFMe~2~}(PPh~3~)~2~] (4), in which the TTF ligand is covalently ligated to platinum via SiMe~2~ 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)