1. A kinetic investigation of reaction of [Os(N)(CH2SiMe3)4][NBun4] with methyl iodide
- Author
-
Zang Yuan. Own and Patricia A. Shapley
- Subjects
chemistry.chemical_classification ,Stereochemistry ,Organic Chemistry ,Enthalpy ,chemistry.chemical_element ,Entropy of activation ,Biochemistry ,Medicinal chemistry ,Inorganic Chemistry ,chemistry.chemical_compound ,chemistry ,Nucleophile ,Oxidation state ,Materials Chemistry ,Osmium ,Physical and Theoretical Chemistry ,Solvent effects ,Alkyl ,Methyl iodide - Abstract
A high oxidation state alkylnitridoosmium complex, [Os(N)(CH2SiMe3)4][NBun4] acts as a nucleophile in reactions with alkyl halides. Alkylimido complexes, Os(NR)(CH2SiMe3)4, are produced. The reaction between [Os(N)(CH2SiMe3)4]− [NBun4] and MeI is second order with k2= 9.5 x 10−5 sect1 M−1 at 23°C in CD2Cl2 under pseudo first order conditions. The entropy of activation, ΔS≠, was found to be −10.6 ± 0.5 cal M−1 K−1 and the enthalpy of activation, ΔH≠, was found to be 19.6 ± 0.2 kcal M−1. The reaction proceeds faster in polar, non-coordinating solvents than in either non-polar solvents or in solvents which can coordinate to the osmium center.
- Published
- 1987