Mechanism of Olefin Epoxidation by Transition Metal Peroxo Compounds | Sciact - CRIS-system of Boreskov Institute of Catalysis

Mechanism of Olefin Epoxidation by Transition Metal Peroxo Compounds Full article

Source

Computational Modeling of Homogeneous Catalysis. Catalysis by Metal Complexes (CMCO, volume 25)
Compilation, Springer New York. NY.2002. 368 c. ISBN 9781402009334. OpenAlex

Output data

Year: 2002, Article number : Ch. 12, Pages count : 35

Tags

Olefin epoxidation, allylic alcohol epoxidation, insertion, direct oxygen, transfer, early transition metals, peroxo and hydroperoxo intermediates, effects, of base ligands, activation barriers, DFT-based calculations

Authors

Rösch Notker ¹ , Di Valentin Cristiana ^1,2 , Yudanov Ilya V. ^1,3

Affiliations

1	Institut für Physikalische und Theoretische Chemie, Technische Universität München, 85747 Garching, Germany
2	Dipartimento di Scienza dei Materiali, Università degli Studi di Milano-Bicocca, via Cozzi 53, 20125 Milano, Italy
3	Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia

Density functional calculations on model systems show that olefin epoxidation by peroxo complexes of early transition metals (Mo, W, Re) in general proceeds by direct transfer via spiro-type transition structures, rather than via insertion. Oxygen transfer by hydroperoxo complexes is at least competitive, if not preferred for Mo, while it is clearly preferred for Ti. A simple MO analysis allows to rationalize many trends (e.g. effects of the metal center and of additional base ligands) found for the computational results.

Rösch N. , Di Valentin C. , Yudanov I.V.
Mechanism of Olefin Epoxidation by Transition Metal Peroxo Compounds
In compilation Computational Modeling of Homogeneous Catalysis. Catalysis by Metal Complexes (CMCO, volume 25). – Springer New York., 2002. – C.289–324. – ISBN 9781402009334. OpenAlex

OpenAlex:

W2021954843

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