Mechanistic Studies of the Reaction of Ir(III) Porphyrin Hydride with 2,2,6,6-Tetramethylpiperidine-1-oxyl to an Unsupported Ir-Ir Porphyrin Dimer.

21:32 EDT 28th August 2014 | BioPortfolio

Summary of "Mechanistic Studies of the Reaction of Ir(III) Porphyrin Hydride with 2,2,6,6-Tetramethylpiperidine-1-oxyl to an Unsupported Ir-Ir Porphyrin Dimer."

Reaction of hydrido[5,10,15,20-tetrakis(p-tolyl)porphyrinato]iridium(III) (Ir(ttp)H) (1) with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) (2) at room temperature gave a 90% yield of the unsupported iridium(II) porphyrin dimer, Ir(II)(2)(ttp)(2) (3). Kinetic measurements revealed that the oxidation followed overall second-order kinetics: rate = k[Ir(ttp)H][TEMPO], k(25 °C) = 6.65 × 10(-4) M(-1). The entropy of activation (ΔS(‡) = -25.3 ± 2.5 cal mol(-1) K(-1)) and the kinetic isotope effect of 7.2 supported a bimolecular associative mechanism in the rate-determining hydrogen atom transfer from Ir(ttp)H to TEMPO.

Affiliation

Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, People's Republic of China.

Journal Details

This article was published in the following journal.

Name: Inorganic chemistry
ISSN: 1520-510X
Pages: 9636-40

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