Structural and mechanistic studies of co-ordination compounds. Part 25. Synthesis and characterization of some octahedral halogeno-amine and -thioether complexes of ruthenium-(II) and -(III)

Abstract

The published methods for the syntheses of trans-[RuLCl2]+ [L = L1, bis(ethane-1,2-diamine); L4, 3,7-diazanonane-1,9-diamine; or L7, 1,4,8,11-tetra-azacyclotetradecane] have been modified. The modified method is highly efficient and reproducible and it has been employed to prepare other trans-[RuLCl2]+ complexes [L = L2, bis(propane-1,3-diamine); L3, bis(NN′-dimethylethane-1,2-diamine); L5, 4,7-diazadecane-1,10-diamine; or L6, 4,8-diazaundecane-1,11-diamine]. Other dihalogeno-complexes, trans-[RuLBr2]+ (L = L1, L2, L4, or L7) and trans-[RuLI2]+ (L = L1 or L4), have been prepared form their corresponding dichloro-complexes through the reactive ruthenium(II) intermediates. Mixed halogeno-complexes of the type trans-[RuL1(X)Y]+ [(X)Y = (Cl) Br, (Cl)l, or (l)Br] have been prepared by metathetical procedures. Meanwhile, some macrocyclic quadridentate thioether complexes trans-[RuLCl2]·2H2O (L = L8, 1,4,8,11-tetrathiacyclotetradecane; or L9, 3,6,10,13-tetrathiabicyclo[13.4.0]nona-1,16,18-triene) and trans-[RuL8Cl2][ClO4]·H2O have also been synthesized. All these complexes are low-spin monomeric species. The electronic and i.r. absorption spectra of these complexes are discussed.