Preparation of Several Homologous Series of Cyclopentadienylruthenium Complexes and Their Solvolysis in Polar Solvents

Abstract
The convenient synthesis of 11 members of a series of compounds RuCl(L)2(η-C5H5) (L = PPh20Me, PPh(OMe)2, P(OMe)3, PPh2Me, PMe(OMe)2, 1/2dppe, PMe3, PPhMe2, PPhEt2, P(OEt)3, P(OPri)3) was accomplished by reaction between an excess of the indicated ligand and RuC1(PPh3)2(η-C5H5) in toluene. Related pentamthylcyclopentadienyl complexes, RuC1(L)2(η-C5Me5) (L - P(to1P)3, 1/2dppe, PMe3, PPh2OMe, PPh(OMe)2, P(OMe)3) were prepared from RuC1(PPh3)2(η-C5Me5) in a similar manner. Exchange of C1 with other anionic groups (X = Br, I, CN, SCN, OCN) in both series was shown to occur in ethanol. Displacement of chloride ion from RUCL(L)2(η-C5H5) or RuCl(L)2(η-C5Me5) by CH3CN or DMSO also occurs in solution in methanol in the presence of NH4PP6, a halide acceptor. This procedure provides excellent yields of the cationic complexes [Ru(solv)(L)2(η-C5H5)]PF6.

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