Reactivity of tungsten(V) mononuclear complexes towards Li(TCNQ) and TCNQ. Comparison of the crystal structures of [W(S2CNMe2)4][TCNQ] and [Mo(S2CNMe2)4][TCNQ]·MeCN (TCNQ = 7,7,8,8-tetracyanoquinodimethane)‡
- 1 January 1998
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 3,p. 489-496
- https://doi.org/10.1039/a707555c
Abstract
The reaction of tungsten(V) complexes [W(S2CNR2)4]I (R = Me or Et) with Li(TCNQ) in a dimethylformamide–water mixture at room temperature afforded the new derivatives [W(S2CNR2)4][TCNQ] 1a and 1b (TCNQ = 7,7,8,8-tetracyanoquinodimethane). These compounds reacted further with TCNQ in acetonitrile to produce [W(S2CNR2)4][TCNQ]2 in which the TCNQ moieties are in a mixed-valence state. The physical properties of these new derivatives in solution and in the solid state are presented. The structures of 1a and of its molybdenum analogue [Mo(S2CNR2)4][TCNQ]·MeCN 2a have been studied by X-ray diffraction analyses: in 1a the TCNQ moieties form alternating stacks along the c axis according to a quite unusual bond–bond overlap; in 2a the TCNQ˙– moieties are dimerized and exhibit the usual slipped conformation.Keywords
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