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 [ ( η 6 - p -cymene ) Ru ( κ 2 - O , O -acac ) ( THF ) ] [ BAr 4 ′ ] ( 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 [ ( η 6 - p -cymene ) Ru ( κ 2 - O , O -acac ) ( THF ) ] [ BAr 4 ′ ] ( 2 ) with KTp {Tp = hydridotris(pyrazolyl)borate} produces [ TpRu ( η 6 - p -cymene ) ] [ BAr 4 ′ ] ( 5 ) . The azide complex [ ( η 6 - p -cymene ) Ru ( κ 2 - O , O -acac ) ( N 3 Ar ) ] [ BAr 4 ′ ] ( 6 ) forms upon reaction of [ ( η 6 - p -cymene ) Ru ( κ 2 - O , O -acac ) ( THF ) ] [ BAr 4 ′ ] ( 2 ) with N3Ar (Ar = p-tolyl), and reaction of [ ( η 6 - p -cymene ) Ru ( κ 2 - O , O -acac ) ( THF ) ] [ BAr 4 ′ ] ( 2 ) with CHCl3 at 100 °C yields the chloride-bridged binuclear complex [ { ( η 6 - p -cymene ) Ru } 2 ( μ -Cl ) 3 ] [ BAr 4 ′ ] ( 7 ) . The details of solid-state structures of [(η6-p-cymene)Ru(κ2-O,O-acac-μ-CH)]2[OTf]2 (1), [ TpRu ( η 6 - p -cymene ) ] [ BAr 4 ′ ] ( 5 ) and [ { ( η 6 - p -cymene ) Ru } 2 ( μ -Cl ) 3 ] [ BAr 4 ′ ] ( 7 ) are disclosed.