Syntheses and characterization of [(η 6-C 6Me 6)Ru(μ-N 3)(X)] 2 (X = N 3 and Cl) complexes and their reactions towards mono- and bidentate ligands

Abstract

The reaction of the complex [{(η 6-C 6Me 6)Ru(μ-Cl)Cl} 2] 1 with sodium azide ligand gave two new dimers of the composition [{(η 6-C 6Me 6)Ru(μ-N 3)(N 3)} 2] 2 and [{(η 6-C 6Me 6)Ru(μ-N 3)Cl} 2] 3, depending upon the reaction conditions. Complex 3 with excess of sodium azide in ethanol yielded complex 2. These complexes undergo substitution reactions with monodentate ligands to yield monomeric complexes of the type [(η 6-C 6Me 6)Ru(X)(N 3)(L)] {X = N 3, Cl, L = PPh 3 ( 4a, 9a); PMe 2Ph ( 4b, 9b); AsPh 3 ( 4c, 9c); X = N 3, L = pyrazole (Hpz) ( 5a); 3-methylpyrazole (3-Hmpz) ( 5b) and 3,5-dimethyl-pyrazole (3,5-Hdmpz) ( 5c)}. Complexes 2 and 3 also react with bidentate ligands to give bridging complexes of the type [{(η 6-C 6Me 6)Ru(N 3)(X)] 2(μ-L)} {X = N 3, Cl, L = 1,2-bis(diphenylphosphino)methane (dppm) ( 6, 10); 1,2-bis(diphenylphosphino)ethane (dppe) ( 7, 11); 1,2-bis(diphenylphosphino)propane (dppp) ( 8, 12); X = Cl, L = 4,4-bipyridine (4,4′-bipy) ( 13)}. These complexes were characterized by FT-IR and FT-NMR spectroscopy as well as by analytical data.The molecular structures of the representative complexes [{(η 6-C 6Me 6)Ru(μ-N 3)(N 3)} 2] 2, [{(η 6-C 6Me 6)Ru(μ-N 3)Cl} 2] 3,[(η 6-C 6Me 6)Ru(N 3) 2(PPh 3)] 4a and [{(η 6-C 6Me 6)Ru(N 3) 2} 2 (μ-dppm)] 6 were established by single crystal X-ray diffraction studies.