Journal
JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume 690, Issue 15, Pages 3522-3528Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2005.02.024
Keywords
oxidative addition; Vaska's complex; ionic liquid; kinetics
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Oxidative addition of methyl iodide to Vaska's complex in the ionic liquids 1-butyl-3-methylimidazolium triflate [C(4)mim][OTT], [C(4)mim] bis(trifluormethylsulfonyl)imide [Tf2N], and N-hexylpyridinium [C(6)Pyr][Tf2N] occurred cleanly to give the expected Ir(III) oxidative addition product. Pseudo-first order rate constants were determined for the oxidative addition reaction in each solvent ([Vaska's] = 0.25 mM, [CH3I] = 37.5 mM). The observed rate constants under these conditions were 5-10 times slower than the rate seen in DMF. At high methyl iodide concentrations (> 23 mM), the expected first order dependence on methyl iodide was not observed. In each ionic liquid, there was no change in the reaction rates within experimental error over the methyl iodide concentration range of 23-75 mM. At lower methyl iodide concentration, a decrease in rate was observed in [C(4)mim][Tf2N] with decreasing concentration of methyl iodide. (c) 2005 Elsevier B.V. All rights reserved.
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