A theoretical study of the mechanism for the homogeneous catalytic reversible dehydrogenation—hydrogenation of nitrogen heterocycles

文献情報

出版日 2011-01-11

DOI 10.1039/C0CP02419H

インパクトファクター 3.676

著者

Xiang-Biao Zhang, Zhao Xi

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要旨

A mechanism for the dehydrogenation reaction of 1,2,3,4-tetrahydroquinoline to quinoline derivatives, catalyzed by a Cp*Ir complex containing a 2-pyridonate ligand, is proposed and supported by theoretical calculations at the B3LYP level. The proposed mechanism involves two stages which are all thermodynamically unfavorable (endothermic by 36.3 kcal mol−1 and 18.4 kcal mol−1, respectively). The apparent activation energies of the first and second stages of the reaction are 30.8 kcal mol−1 and 34.0 kcal mol−1, respectively, and are considered overestimates of the entropy change of reaction. Owing to a decrease in the oxidative ability of iridium(III) coordinated to large electronegative nitrogen and chlorine, ligand promoted hydrogen abstraction is crucial at both stages of dehydrogenation, in which the oxidation state of iridium(III) does not change, and the ligand 2-pyridonate is converted to 2-hydroxypyridine. Cp*Ir(C5NH4OH)ClH, an important intermediate, releases hydrogen through an energy barrier of 23.5 kcal mol−1.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

A theoretical study of the mechanism for the homogeneous catalytic reversible dehydrogenation—hydrogenation of nitrogen heterocycles

文献情報

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掲載誌

Physical Chemistry Chemical Physics

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