CYCLOPENTADIENYL-RUTHENIUM AND -OSMIUM COMPLEXES III. CHEMICAL MECHANISM OF DISSOLUTION OF CHLORO(η-CYCLOPENTADIENYL)-BIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II) IN POLAR SOLVENTS

Article abstract of DOI:10.1016/0022-328X(85)80435-6

The conversion of CpRuCl(PPh3)2 in boiling ethylene glycol within 90 h of reflux has been investigated.New complex cations in the form of their tetraphenylborates, for which the formulae 1RuCl(PPh3)PPh2Cp²Ru(η-C6H5)>⁺ and ⁺ are proposed, were isolated.The former cation is also formed at lower temperatures during the reflux of CpRuCl(PPh3)2 in methanol.The following process takes place: 2CpRuCl(PPh3)2 -> 1RuCl(PPh3)PPh2Cp²Ru(η-C6H5)>⁺ + Cl^- + 2PPh3.In the presence of dicyclopentadiene during the reflux of CpRuCl(PPh3)2 in high boiling polar solvents (ethylene glycol, dimethyl sulphoxide), ruthenocene is formed in a 90 percent yield.One of the cyclopentadienyl groups in ruthenocene originates from dicyclopentadiene.As a result of the reaction of CpRuCl(PPh3)2 and NaBPh4 in a mixture of diglyme and methanol, a colourless, crystalline compound, CpRu(η-C6H5)BPh3, is obtained in a 50-60 percent yield.