First heteroleptic Mo3S7 clusters containing non-innocent phenanthroline ligands

Abstract

Reaction of the thiobromide [Mo 3 S 7 Br 6 ] 2− cluster anion with 5,6-dimethyl-1,10-phenanthroline (Me 2 Phen) in solution leads to the substitution of two bromide ligands and the subsequent formation of a new mixed-ligand neutral complex [Mo 3 S 7 Br 4 (Me 2 Phen)] (I). Reaction of [Mo 3 S 7 Br 6 ] 2− with 5,6-dimethyl-1,10-phenanthroline in CH 2 Cl 2 followed by treatment of I with Na(Dtc) · 3H 2 O (Dtc = diethyldithiocarbamate) results in the new mixed-ligand cluster complex [Mo 3 S 7 (Dtc) 2 (Me 2 Phen)] 2+ ( IIa ). Slow evaporation of the CHCl 3 solution of the complex in the presence of PF − 6 gives crystals of {[Mo 3 S 7 (Dtc) 2 (Me 2 Phen)]Br}PF 6 · 3CHCl 3 ( II ) characterized by X-ray structural analysis. Close contacts S...S result in the formation of cationic dimers {[Mo 3 S 7 (Dtc) 2 (Me 2 Phen)] 2 } 4+ which form infinite chains through additional S ax ...Br contacts. All compounds were characterized by IR, elemental analysis and ESI-MS. Synthesized complexes represent the first examples of heteroleptic Mo 3 S 7 clusters containing phenanthroline ligands.