An electron spin resonance and optical study of the behaviour of Cs2[TcNCl5] in hydrochloric acid solutions
- 1 January 1988
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 10,p. 2585-2589
- https://doi.org/10.1039/dt9880002585
Abstract
Optical spectroscopy, magnetic susceptibility, and e.s.r. have been used to study the behaviour of Cs2[TcNCl5] in aqueous HCl solutions. In 5.6 mol dm–3 HCl the predominant species is the [TcNCl4]– anion (λmax 398 nm, ε 440 m2 mol–1) possibly with H2O weakly bound trans to the N atom. Addition of 1 volume of H2O to Cs2[TcNCl5] followed by 2 volumes of 5 mol dm–3 HCl gives a deep blue species (λmax. 558 nm, ε 393 m2 mol–1), which is converted to [TcNCl4]– on standing. Cs2[TcNCl5] dissolved in 0.5 mol dm–3 HCl gives a pink solution (λmax. 540 nm, ε 215 m2 mol–1) which is stable over several days. The magnetic susceptibility and e.s.r. measurements indicate that the blue and pink species are diamagnetic. Possible structures of the diamagnetic species are discussed by analogy to the behaviour of [MOX5]n– in solutions of varying acidity.Keywords
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