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

Direct reactions between HSC 6 H 2 Cl 2 SH, FeCl 3 ·6H 2 O and divalent metal bases lead to the formation of the cation–anion metal–dithiolene complexes [Ca(H 2 O) 3 (OCMe 2 ) 4 ][Fe 2 (SC 6 H 2 Cl 2 S) 4 ]·3OCMe 2 and [Zn(DMF) 6 ][Fe 2 (SC 6 H 2 Cl 2 S) 4 ], as well as the molecular compound [Ba(OCMe 2 ) 6 ][Fe 2 (SC 6 H 2 Cl 2 S) 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 K 2 [Fe 2 (SC 6 H 2 Cl 2 S) 4 ] and ZnCl 2 ·6H 2 O or NiCl 2 ·6H 2 O was also evaluated, giving rise to the ion-pair compounds [Fe(H 2 O) 2 (THF) 4 ][Ni(SC 6 H 2 Cl 2 S) 2 ] 2 ·4THF and [Fe(H 2 O) 4 (THF) 2 ][Fe 2 (SC 6 H 2 Cl 2 S) 4 ]·4THF and the coordination polymer {[K 2 (THF) 8 ][Zn 6 (μ-Cl) 2 (SC 6 H 2 Cl 2 S) 4 (μ-κO:κO′-SC 6 H 2 Cl(ClO 2 )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.