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Issue 9, 2019
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Synthesis and structural characterization of transition metal dithiolene derivatives containing divalent metals as counter-cations

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Abstract

Direct reactions between HSC6H2Cl2SH, FeCl3·6H2O and divalent metal bases lead to the formation of the cation–anion metal–dithiolene complexes [Ca(H2O)3(OCMe2)4][Fe2(SC6H2Cl2S)4]·3OCMe2 and [Zn(DMF)6][Fe2(SC6H2Cl2S)4], as well as the molecular compound [Ba(OCMe2)6][Fe2(SC6H2Cl2S)4], instead of metal–dithiolene coordination polymers as compared with results previously obtained when alkali metals, under similar conditions, were used. An alternative synthetic route based on the reactions between K2[Fe2(SC6H2Cl2S)4] and ZnCl2·6H2O or NiCl2·6H2O was also evaluated, giving rise to the ion-pair compounds [Fe(H2O)2(THF)4][Ni(SC6H2Cl2S)2]2·4THF and [Fe(H2O)4(THF)2][Fe2(SC6H2Cl2S)4]·4THF and the coordination polymer {[K2(THF)8][Zn6(μ-Cl)2(SC6H2Cl2S)4(μ-κO:κO′-SC6H2Cl(ClO2)S)2]}n. It is interesting to remark that in the last compound the oxidation of one Cl substituent of a dithiolene ligand resulted in the formation of a Cl(O)2 group.

Graphical abstract: Synthesis and structural characterization of transition metal dithiolene derivatives containing divalent metals as counter-cations

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Supplementary files

Article information


Submitted
08 Nov 2018
Accepted
22 Jan 2019
First published
23 Jan 2019

CrystEngComm, 2019,21, 1423-1432
Article type
Paper

Synthesis and structural characterization of transition metal dithiolene derivatives containing divalent metals as counter-cations

O. Castillo, E. Delgado, D. Hernández, E. Hernández, A. Martín and F. Zamora, CrystEngComm, 2019, 21, 1423
DOI: 10.1039/C8CE01916A

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