Alkene Epoxidation Catalyzed by Ti-Containing Polyoxometalates: Unprecedented β‑Oxygen Transfer Mechanism | Sciact - CRIS-system of Boreskov Institute of Catalysis

Alkene Epoxidation Catalyzed by Ti-Containing Polyoxometalates: Unprecedented β‑Oxygen Transfer Mechanism Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Output data

Year: 2016, Volume: 55, Number: 12, Pages: 6080-6084 Pages count : 5 DOI: 10.1021/acs.inorgchem.6b00621

Tags

MOLECULAR-ORBITAL METHODS; AB-INITIO; OLEFIN EPOXIDATION; OXIDATION; TITANIUM; DENSITY; H2O2; DFT; REACTIVITY; TITANOSILICATES

Authors

Jimenez-Lozano Pablo ¹ , Skobelev Igor Y. ^2,3 , Kholdeeva Oxana A. ^2,3 , Poblet Josep M. ¹ , Carbo Jorge J. ¹

Affiliations

1	Department de Química Física i Inorganica, Universitat Rovira i Vigili, Marcel ̀ ·lí Domingo s/n, 43007 Tarragona, Spain
2	Boreskov Institute of Catalysis, Prospekt Akademika Lavrentiev 5, Novosibirsk 630090, Russia
3	Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia

Funding (3)

1	Federal Agency for Scientific Organizations	V.44.2.2.
2	Government of Catalonia	2014SGR199
3	Ministry of Economic Affairs and Digital Transformation	CTQ2014-52774-P

A DFT study revealed that the mechanism of alkene epoxidation with hydrogen peroxide catalyzed by Ti-containing polyoxometalates (POMs) depends on the Ti coordination environment: For rigid and hindered Ti centers, the unprecedented β-oxygen transfer from the titanium hydroperoxo species becomes favored over the α-oxygen one. Improving the model for catalyst description, the calculations were able to reproduce the Arrhenius activation energy values determined in kinetic studies. Unlike protonation, the possible ion-pairing between POMs and countercations has a minor effect on the electrophlicity of the catalyst and, consequently, on the activity of epoxidation.

Jimenez-Lozano P. , Skobelev I.Y. , Kholdeeva O.A. , Poblet J.M. , Carbo J.J.
Alkene Epoxidation Catalyzed by Ti-Containing Polyoxometalates: Unprecedented β‑Oxygen Transfer Mechanism
Inorganic Chemistry. 2016. V.55. N12. P.6080-6084. DOI: 10.1021/acs.inorgchem.6b00621 WOS Scopus РИНЦ ANCAN PMID OpenAlex

Submitted:	Mar 11, 2016
Published online:	May 27, 2016
Published print:	Jun 20, 2016

Web of science:	WOS:000378369900044
Scopus:	2-s2.0-84975482349
Elibrary:	27138564
Chemical Abstracts:	2016:866171
Chemical Abstracts (print):	165:31133
PMID:	27232155
OpenAlex:	W2408133551

DB	Citing
Web of science	42
Scopus	46
Elibrary	37
OpenAlex	46