title: Phosphine substitution reactions of (η5-cyclopentadienyl)ruthenium bis(triarylphosphine) chloride, CpRu(PAr3)2Cl {PAr3 = PPh3, P(p-CH3C6H4)3, P(p-FC6H4)3, P(p-CH3OC6H4)3, and PPh2(p-CH3C6H4)}: a tale of two mechanisms.
abstract: The kinetics of phosphine substitution in CpRu(PAr3)2Cl by PMePh2 under pseudo-first order conditions in CDCl3 have been measured for PAr3 = PPh3, 1a, PPh2(p-tol), 1b, P(p-tol)3, 1c, P(p-CH3OC6H4)3, 1d, and P(p-FC6H4)3), 1e. Activation parameters characteristic of a dissociative pathway (ΔH(†) = 110-124 ± 2 kJ mol(-1), ΔS(†) = 16-44 ± 5-12 J mol(-1) K(-1)) are observed for all five compounds. The rate of substitution in CpRu(PAr3)2Cl (1a) and CpRu[P(p-FC6H4)3]2Cl (1e) is independent of added chloride ion and decreases in the presence of excess PAr3, however, the rate of substitution in CpRu[P(p-CH3OC6H4)3]2Cl (1d) is first order in added chloride ion and is less dependent on added PAr3. A mechanism involving [CpRu(PAr3)2(PMePh2)](+)[Cl](-) intermediates contributes to the substitution in 1b-d.
authors.affiliation: Department of Chemistry, Colby College, Waterville, ME 04901, USA.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Verschoor-Kirss
authors.forename: Olivia
authors.initials: O
authors.lastname: Hendricks
authors.forename: Lawrence
authors.initials: L
authors.lastname: Renna
authors.forename: David
authors.initials: D
authors.lastname: Hill
authors.forename: Rein U
authors.initials: RU
authors.lastname: Kirss