POLYOXOANION-SUPPORTED, ATOMICALLY DISPERSED CYCLOOCTADIENERUTHENIUM(II) COMPLEXES

The cation [Ru(C8H12)]2+ was supported on [P3O9]3-, [V4O12]4- and [Nb2W4O19]4- polyoxoanions. All the complexes were stable in air and were characterized by elemental and thermogravimetric analysis, IR, H-1, C-13 and P-31 NMR spectroscopy. The crystal and molecular structure of [NBu4][Ru(C8H12)(MeCN)-(P3O9)].Et2O has been determined [space group C2/c, a = 38.359(4), b = 9.907(5), c = 26.437(3) angstrom, beta = 127.720(4)-degrees]. Ruthenium(II) is octahedrally co-ordinated to the two C8H12-diene groups, to one acetonitrile molecule and through three O atoms to the P3O93- ligand. In the case of [Ru(C8H12)(MeCN)2-(HV4O12)]- and [Ru(C8H12)(MeCN)2(V4O12)]2- where a bidentate co-ordination to the polyanion is observed, two MeCN molecules are co-ordinated by Ru, resulting in the 18-valence-electron configuration. The [Nb2WO19]4- anion behaves differently: its reaction with [RuCl(C8H12)(MeCN)3]PF6 leads to a product which, on the basis of IR, elemental analysis and the literature, we formulate as [NBu4]3[{RuCl(C8H12)(MeCN)}5(Nb2W4O19)2].3H2O. In this case two Nb2W4O194- anions are probably linked, face to face, by five organometallic centres.