Reaction between cyclopentadienyl ruthenium bi(triphenylphosphine)chloride, CpRu(PPh3)2Cl, and acetyl iodide or methyl iodide yields CpRu(PPh3)2I in nearly quantitative yield. The reaction with acetyl iodide involves a radical pathway while the mechanism of the reaction with methyl iodide has not been explored. The rate constant for halide exchange between CpRu(PPh3)2Cl and CH3I under pseudo-first order conditions at 40°C is kobs= 2.8± 0.4 x 10-5 s-1 , similar to the rate of phosphine substitution. The rate is independent of the concentration of methyl iodide and unchanged in the presence of excess iodide ion. These data argue for mechanism where phosphine dissociation is the rate determining step. We will also report on progress in distinguishing radical mechanisms from oxidative addition and/or s-bond metathesis pathways.

Kinetics and mechanism of halide exchange between CpRu(PPh3)2Cl and methyl iodide

256th National Meeting (2018)

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