Structural Study of the Compounds Formed in the Reactions of FeCl3·6H2O with Ni(OH)2 in the Presence of Dithiolenes HSRSH (R = C6H2Cl2 or C6H4).

Esther Delgado,María Pérez,Josefina Perles,Félix Zamora,Elisa Hernández

doi:10.3390/molecules25092240

Abstract

In our attempts to prepare coordination polymers by reaction of FeCl3·6H2O and Ni(OH)2 in the presence of dithiolenes HSC6H2X2SH (X = Cl or H), several ion pairs of compounds containing the anionic entity [Ni(SC6H2X2S)2]− were obtained instead. It was also found that other species without dithiolene ligands were formed in these reactions, giving rise to different ion pairs and a tetrametallic cluster. The careful isolation of the different types of crystalline solids allowed the characterization of all of the resulting compounds by single crystal X-ray diffraction (SCXRD). In order to establish the amount of nickel and iron present in the crystals, complementary total reflection X-ray fluorescence (TXRF) analyses were performed. The eight different structural types that were obtained are described and compared with related ones found in the literature.

Highlights

The chemistry of transition metals with dithiolene derivatives is a research field of high interest due to the outstanding physical properties that these compounds can show, as well as their wide structural diversity [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15]
We have previously studied the influence of several parameters, such as the nature of the dithiolene ligands, the size of the counter cations, the influence of crystallization conditions, as well as the type of iron precursor used, in the synthesis of a series of coordination polymers (CPs) containing the dianionic entities [Fe2 (SC6 H2 X2 S)4 ]2− (X = Cl or H) and [M2 (μ-L)n ]2+
Cl2 S)4 ] and different alkali metals [20] failed in our attempts to prepare CPs with the same dianionic dianionic andmetals divalent metals such Ba(II)

Summary

Introduction

The chemistry of transition metals with dithiolene derivatives is a research field of high interest due to the outstanding physical properties that these compounds can show, as well as their wide structural diversity [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15]. We described the syntheses of some ion-pair molecules instead of CPs, when divalent cations such as Ca(II), Ba(II), and Zn(II) were used [20]. Taking into account these results, we evaluated whether the Ni(II) cation, that shows high ability to coordinate to sulfur atoms, could act as a linker between the anionic entities [Fe2 (SC6 H2 X2 S)4 ]2− (X = Cl or H) in order to prepare CPs. we report on the syntheses and crystal structures of the new compounds [Ni(DMF)6 ][Ni(SC6 H2 Cl2 S)2 ]2 ·2DMF (1), [Ni(DMF)6 ]

Methods

Discussion

Conclusion