Ruthenium(II) complexes possessing the η6-p-cymene ligand

Complexes possessing a soft donor η6-arene and hard donor acetylacetonate ligand, [(η6-p-cymene)Ru(κ2-O,O-acac-μ-CH)]2[OTf]2 (1) (OTf = trifluoromethanesulfonate; acac = acetylacetonate) and [(η6-p-cymene)Ru(κ2-O,O-acac)(THF)][BAr4′](2) {Ar′ = 3,5-(CF3)–C6H3}, were prepared and fully characterized. The lability of the μ-CH linkage for complex 1 and the THF ligand of 2 allow access to the unsaturated cation [(η6-p-cymene)Ru(κ2-O,O-acac)]+. The reaction of [(η6-p-cymene)Ru(κ2-O,O-acac)(THF)][BAr4′](2) with KTp {Tp = hydridotris(pyrazolyl)borate} produces [TpRu(η6-p-cymene)][BAr4′](5). The azide complex [(η6-p-cymene)Ru(κ2-O,O-acac)(N3Ar)][BAr4′](6) forms upon reaction of [(η6-p-cymene)Ru(κ2-O,O-acac)(THF)][BAr4′](2)with N3Ar (Ar = p  -tolyl), and reaction of [(η6-p-cymene)Ru(κ2-O,O-acac)(THF)][BAr4′](2) with CHCl3 at 100 °C yields the chloride-bridged binuclear complex [{(η6-p-cymene)Ru}2(μ-Cl)3][BAr4′](7). The details of solid-state structures of [(η6-p-cymene)Ru(κ2-O,O-acac-μ-CH)]2[OTf]2 (1), [TpRu(η6-p-cymene)][BAr4′](5) and [{(η6-p-cymene)Ru}2(μ-Cl)3][BAr4′](7) are disclosed.

The graphic displays the solid-state structure of [(η6-p-cymene)Ru(κ2-O,O-acac-μ-CH)]2[OTf]2 (acac = acetylacetonate). This complex and [(η6-p-cymene)Ru(κ2-O,O-acac)(THF)]+ provide precursors to a series of η6-p-cymene complexes that have been fully characterized including single-crystal X-ray diffraction studies and cyclic voltammetry.Figure optionsDownload as PowerPoint slide