Reactivity of dinuclear arene ruthenium complexes: reactions of the hydrido complex [(p-Me-C6H4-Pri)2Ru2Cl2(μ-Cl)(μ-H)] with NaX and HX (X=F, Cl, Br, I)

The dinuclear hydrido complex [(p-Me-C6H4-Pri)2Ru2Cl2(μ-Cl)(μ-H)] (1) reacts with the sodium halides NaX in methanol to give the halogen analogues [(p-Me-C6H4-Pri)2Ru2X2(μ-X)(μ-H)] (2: X=F, 3: X=Br, 4: X=I). With HX, complex 1 reacts to give the tetrahalo complexes [(p-Me-C6H4-Pri)2Ru2X2(μ-X)2] (5: X=Cl, 6: X=Br, 7: X=I); in the case of X=I, a large excess of HI leads to the formation of the cationic complex [(p-Me-C6H4-Pri)2Ru2(μ-I)3]+ (8). The X-ray structure analysis of 1 shows a dinuclear Ru2 backbone with two terminal chloro ligands being trans with respect to each other as the two p-cymene ligands, the two bridging ligands lie in a plane perpendicular to the plane defined by the terminal chloro ligands and the ruthenium atoms.