INDENYL COMPLEXES OF RUTHENIUM(II). CRYSTAL STRUCTURE OF 5-C9H7)>ClO4.1/2CH2Cl2

Article abstract of DOI:10.1016/0022-328X(85)88033-5

The compound 5-C9H7)> (I) has been made in high yield by reaction of with indene and potassium hydroxide in ethanol and its reactions have been examined.Complex I reacts with appropriate nucleophiles to give the complexes 5-C9H7)> (X=H, CH3, I, SnCl3, C2Ph) and 5-C9H7)>.Heating of complex I with methanol in a sealed tube leads to the elimination of the indenyl group and decarbonylation of methanol.Cationic complexes of formulae 5-C9H7)>ClO4 (L=CH3CN, 2-ClC6H4CN, CH2=CHCN, 1,2-(CN)2C6H4, C2H4(CN)2, N2H4, CNBu^t, CO, C=CHPh, and C2H4) and 5-C9H7)>ClO4 (L-L=2,5-norbornadiene (nbd), tetrafluorobenzobarrelene (tfb), ethylenediamine (en), propylenediamine (pn), biimidazole (Hbim), 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen)) are obtained by treatment of complex I with the appropriate ligand and sodium perchlorate in methanol.Reaction of the vinylideneruthenium complex 1-C=CHPh)(PPh3)2(η⁵-C9H7)>ClO4 with oxygen gives 5-C9H7)>ClO4.The structure of 5-C9H7)>ClO4.1/2CH2Cl2 has been determined by X-ray diffraction.The space group is P<*> with lattice constants a 18.5513(14), b 12.9165(5), and c 9.6898(5) Angstroem, and α 80.942(5), β 104.998(7) and γ 111.130(4) deg.Final R and R_w factors are 0.039 and 0.043, respectively, for the 6836 observed data (3?(I) criterion).The metal is bonded to an indenyl group through the five-membered ring, and hexacoordination of the ruthenium atom is completed by two triphenylphosphine ligands and a carbonyl group.