Preparations of Cyclopentadienylruthenium Complexes with Trimethylphosphine Ligands

Abstract

The reaction of Ru(C, -H ₅)(PPh ₃) ₂Cl with PMe ₃ in the polar solvent EtOH, followed by metathesis, gives [Ru(C ₅H ₅)(PPh ₃) ₂(PMe ₃)]PF ₆. However in a less polar solvent, toluene, the reaction proceeds in a different manner, giving Ru(C ₅H ₅)(PMe ₃) ₂Cl. A reaction with dpe occurs in a similar fashion to give Ru(CrHg)(dpe)Cl. The compounds, Ru(C ₅H ₅)(PMe ₃) ₂X (X = Br, I, SCN), can be prepared from the chloride complex by anion exchange, and the compound with x = SnCU can be prepared by addition of SnCl ₂ to this precursor. Ionic complexes [Ru(C ₅H ₅)(PMe ₃) ₂L]X (L = PMe ₃, CO, PPh ₃) are formed from Ru(CgH ₅)-(PMe ₃) ₂Cl and these several ligands in polar solvents; these cations were metathesized with NHPF, and isolated as PF, salts. The reaction of Ru(C ₅H ₅)(PMe ₃) ₂Cl with AgBF ₄ in MeCN gives [Ru(C ₅H ₅)(PMe ₃) ₂(MeCN)]BF ₄and the reaction with NOPF & gives [Ru(C ₅H ₅)(PMe ₃) ₂(NO)](PF ₆) _2> The reaction of Ru(C ₅H ₅)(CO) ₂Cl with PMe ₃ gives predominately [Ru(C ₅H ₅)(CO)-(PMe₃)₂]⁺ whereas the reaction of Ru(C₅H₅)(CO₂)I with PMe₃ gives a mixture containing [Ru(C₅H₅)(CO)₃-x(PMe₃)x] + (x[dbnd]1,2) Ru(C₅H₅)(CO)(PMe₃)I. The complex Ru(C₅H₅)(CO)(PMe₃)]PF₆ is best prepared by displacement of MeCN from [Ru(C₅H₅)(CO)₂, (MeCN)]PF₆.