CYCLOPENTADIENYLRUTHENIUM COMPLEXES WITH CHELATING DIAMINES AND DIOLEFINS. CRYSTAL STRUCTURES OF ClO4 AND 6-C6H5)Ph2PO>(η-C5H5)>ClO4. A NEW MODE OF COORDINATION OF TRIPHENYLPHOSPHINE OXIDE

Article abstract of DOI:10.1016/S0022-328X(00)99209-X

Complexes of the general formulae ClO4 and ClO4 (diamine=ethylendiamine (en), propylenediamine (pn), 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), biimidazole (H2bim), bibenzimidazole (H2bbzim) and 2-(2'-pyridylbenzimidazole) (Hpybzim); diolefin=2,5-norbornadiene (nbd), tetrafluorobenzobarrelene (tfb)) have been made by reaction of the complex RuCl(PPh3)2(η-C5H5) with the diamine or diolefin in the presence of sodium perchlorate.A single-crystal X-ray diffraction study of ClO4 has been carried out.Crystals of the complex are monoclinic, space group P2₁/n, with a 18.0576(5), b 14.5070(3), c 10.3186(3) Angstroem; β 103.20(6)^o.The structure was solved by Patterson synthesis using 4209 observed reflections (2?(I) criterion) and refined to a R factor of 0.040.Reaction of RuCl(PPh3)2(η-C5H5) with oxygen in the presence of sodium perchlorate leads to oxidation of the coordinated triphenylphosphine ligands giving the complex 6-C6H5)Ph2PO>(η-C5H5)>ClO4.In order to establish the structural identity of this compound a single-crystal X-ray diffraction study has been made.Crystals of this complex are monoclinic, space group P2₁/c, with a 10.8182(5), b 9.4480(3), c 21.0036(19) Angstroem; β 90.246(6)^o.The structure was solved by Patterson synthesis using 3819 observed reflections (3?(I) criterion) and refined to a R factor of 0.036.The ruthenium atom is coordinated in a sandwich fashion by the cyclopentadienyl group and a phenyl ring of the triphenylphosphine oxide ligand.The synthesis of new heteronuclear ruthenium(II)-rhodium(I) complexes of formulae <(η-C5H5)(Ph3P)Ru(μ-bim)RhY2>x (x=2 or 1) and (η-C5H5)(Ph3P)Ru(μ-bbzim)RhY2 (Y=CO, Y2=diolefin) is also described.