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.

06:00 EDT 21st September 2010 | 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.


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


DeepDyve research library

PubMed Articles [18179 Associated PubMed Articles listed on BioPortfolio]

Detailed Mechanistic Studies on Palladium Catalyzed Selective C-H Olefination with Aliphatic Alkenes: A Significant Influence of Proton Shuttling.

Directing group assisted regioselective C-H olefination with electronically biased olefins are well studied. However, the incorporation of unactivated olefins has remained largely unsuccessful. A prop...

β-Hydride Elimination at Low-Coordinate Gold(III) Centers.

This article reports the first comprehensive study of β-hydride elimination at gold(III). The stability/fate of gold(III) alkyl species have been investigated experimentally and computationally. A se...

Rational Design in Catalysis: A Mechanistic Study of β-Hydride Eliminations in Gold(I) and Gold(III) Complexes Based on Features of the Reaction Valley.

β-Hydride eliminations for ethylgold(III) dichloride complexes are identified as reactions with an unusually long prechemical stage corresponding to the conformational preparation of the reaction com...

Hydrodehalogenation of Haloarenes by a Sodium Hydride-Iodide Composite.

A simple protocol for hydrodebromination and -deiodination of halo(hetero)arenes was enabled by sodium hydride (NaH) in the presence of lithium iodide (LiI). Mechanistic studies showed that an unusual...

Mechanistic Studies of the Photoinduced Quinone Trimethyl Lock Decaging Process.

Mechanistic studies of a general reaction that decages a wide range of substrates on exposure to visible light are described. The reaction involves a photochemically initiated reduction of a quinone m...

Clinical Trials [1384 Associated Clinical Trials listed on BioPortfolio]

Physiopathology of Pulmonary Arterial Hypertension: Mechanistic Studies

The current aims to combine analysis of different inflammatory biomarkers and BMPR2 mutations, which are currently analyzed in each patient diagnosed with idiopathic or familial PAH, to es...

ADD-ON Study to Existing Hypoparathyroidism Studies

The purpose of this protocol is to add on additional exploratory studies to investigate changes in bone quality parameters with PTH(1-84) treatment of hypoparathyroidism. In addition to t...

Mechanistic Effects of Colchicine in Patients With Myocardial Infarction

The aim of this study is to determine the immuno-modulatory mechanistic effects of colchicine in patients with myocardial infarction (MI). Investigators hypothesize that colchicine exerts ...

Montelukast in ENL Reaction

Objective of the trial is to assess the safety and efficacy of Montelukast in treatment of Erythema Nodosum leprosum (ENL) reaction in multibacillary leprosy patients either in combination...

Systemic, Intrapulmonary and Pleural Inflammatory Reaction in Patients Undergoing Thoracic Surgery

Inflammatory reaction in different compartments of the body may have a negative effect on outcome. This study assesses the inflammatory reaction systemically, intrapulmonary and intrapleur...

Medical and Biotech [MESH] Definitions

Studies designed to examine associations, commonly, hypothesized causal relations. They are usually concerned with identifying or measuring the effects of risk factors or exposures. The common types of analytic study are CASE-CONTROL STUDIES; COHORT STUDIES; and CROSS-SECTIONAL STUDIES.

Cyclic N-oxide radical functioning as a spin label and radiation-sensitizing agent.

Studies in which the presence or absence of disease or other health-related variables are determined in each member of the study population or in a representative sample at one particular time. This contrasts with LONGITUDINAL STUDIES which are followed over a period of time.

Inflammation of an intervertebral disk or disk space which may lead to disk erosion. Until recently, discitis has been defined as a nonbacterial inflammation and has been attributed to aseptic processes (e.g., chemical reaction to an injected substance). However, recent studies provide evidence that infection may be the initial cause, but perhaps not the promoter, of most cases of discitis. Discitis has been diagnosed in patients following discography, myelography, lumbar puncture, paravertebral injection, and obstetrical epidural anesthesia. Discitis following chemonucleolysis (especially with chymopapain) is attributed to chemical reaction by some and to introduction of microorganisms by others.

Antibodies that can catalyze a wide variety of chemical reactions. They are characterized by high substrate specificity and share many mechanistic features with enzymes.

Quick Search

DeepDyve research library

Searches Linking to this Article