Synthesis and characterization of iron(2+) and ruthenium(2+) diimino-, diamino- and diamido-diphosphine complexes X-ray crystal structure of trans-RuCl2(P2N2C2H4)center dot CHCl3

摘要

The interaction of Ru(OAc)(2)(Ph(3)P)(2) with one equivalent of N,N'-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (P2N2C2) in refluxing dichloromethane gave trans-Ru(OAc)(2)(P2N2C2). 2H(2)O (I) in moderate yield (63%); in refluxing-toluene, it gave a red solid which upon recrystallization in CHCl3 gave trans-RuCl2(P2N2C2). 2H(2)O (II) in good yield (92%). Compound II could also be prepared in good yield (85%) via the interaction of RuCl2(DMSO)(4) with one equivalent of P2N2C2 in refluxing toluene. The interaction of RuCl2(DMSO)(4) with one equivalent of N,N'-bis[o-(diphenylphosphino) benzylidene]-1,3-diaminopropane (P2N2C3), N,N'-bis[o-(diphenylphosphino)benzyl] ethylenediamine (P2N2C2H4) and N,N'-bis[o-(diphenylphosphino)benzamido]ethane (PN2C2-amide) in refluxing toluene gave trans-RuCl2(P2N2C3) (III), trans-RuCl2(P2N2C2H4) (IV) and trans-RuCl2(P2N2C2-amide) (V) in good yield, respectively. The interaction of Fe(ClO4)(2) . 6H(2)O with one equivalent of P2N2C2 and P2N2C2H4 in refluxing acetonitrile gave trans-[Fe(P2N2C2)(CH3CN)(2)](ClO4)(2) (VI) and trans-[Fe(P2N2C2])(CH3CN)(2)](ClO4)(2) (VII), respectively. Interaction of FeCl2 . 4H(2)O with one equivalent of N,N'-bis[o-(diphenylphosphino)benzyliden]-1,6-diaminohexane (P2N2C6) in refluxing gave trans-FeCl2(P2N2C6) (VIII). Complexes I-VIII have been fully characterized by analytical and spectroscopic methods. The structure of IV has been established by an X-ray diffraction study. Compound II could be reduced to compound IV with NaBH4 in ethanol and oxidized to V with aqueous H2O2 acetonitrile. Catalytic studies showed that both II and IV were effected catalysts for the hydrogenation of acrylic acid to propionic acid.