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

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.