Synthesis and characterization of half-sandwich iridium complexes containing 2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene and ancillary ortho-carborane-1,2-dichalcogenolato ligands

The binuclear half-sandwich iridium complexes {Cp∗IrCl2}2(μ-2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene) (3) and {Cp∗Ir[E2C2(B10H10)]}2(μ-2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene) (E = S(5a), Se(5b)) were prepared from the reaction of [Cp∗IrCl(μ-Cl)]2 or the “pseudo-aromatic” half-sandwich iridium complex Cp∗Ir[E2C2(B10H10)] (E = S(4a), Se(4b)) with a tetrathiafulvalene (TTF) derivative 2,6-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene (2) at room temperature. The complexes (3, 5a and 5b) have been fully characterized by IR and NMR spectroscopy, as well as elemental analysis. And the molecular structures of 2 and 5a were established through X-ray crystallography. It is interesting that infinite tunnels are created by repeating ‘buckled bowl’ molecules of 5a.