Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies
Epoxidation of a range of alkenes with aqueous H2O2 easily proceeds in the presence of the dititanium-containing 19-tungstodiarsenate(III) [Ti2(OH)2As2W19O67(H2O)]8– (1), which contains five-coordinate Ti atoms. The results of product and kinetics studies support a mechanism that involves a reversib...
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2010
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| Online Access: | http://hdl.handle.net/10725/17247 https://doi.org/10.1002/ejic.201000615 http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.php https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/ejic.201000615 |
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| _version_ | 1864513474034401280 |
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| author | Donoeva, Baira G. |
| author2 | Trubitsina, Tatiana A. Antonova, Nadya S. Carbo, Jorge J. Poblet, Josep M. Al-Kadamany, Ghada Ulrich, Kortz Kortz, Ulrich Kholdeeva, Oxana A. |
| author2_role | author author author author author author author author |
| author_facet | Donoeva, Baira G. Trubitsina, Tatiana A. Antonova, Nadya S. Carbo, Jorge J. Poblet, Josep M. Al-Kadamany, Ghada Ulrich, Kortz Kortz, Ulrich Kholdeeva, Oxana A. |
| author_role | author |
| dc.creator.none.fl_str_mv | Donoeva, Baira G. Trubitsina, Tatiana A. Antonova, Nadya S. Carbo, Jorge J. Poblet, Josep M. Al-Kadamany, Ghada Ulrich, Kortz Kortz, Ulrich Kholdeeva, Oxana A. |
| dc.date.none.fl_str_mv | 2010 2010-10-15 2025-09-11T11:50:21Z 2025-09-11T11:50:21Z |
| dc.identifier.none.fl_str_mv | 1434-1948 http://hdl.handle.net/10725/17247 https://doi.org/10.1002/ejic.201000615 Donoeva, B. G., Trubitsina, T. A., Antonova, N. S., Carbó, J. J., Poblet, J. M., Al‐Kadamany, G., ... & Kholdeeva, O. A. (2010). Epoxidation of Alkenes with H 2 O 2 Catalyzed by Dititanium‐Containing 19‐Tungstodiarsenate (III): Experimental and Theoretical Studies. European Journal of Inorganic Chemistry, 2010(33), 5312-5317. http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.php https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/ejic.201000615 |
| dc.language.none.fl_str_mv | en |
| dc.relation.none.fl_str_mv | European Journal of Inorganic Chemistry |
| dc.rights.*.fl_str_mv | info:eu-repo/semantics/openAccess |
| dc.title.none.fl_str_mv | Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies |
| dc.type.none.fl_str_mv | Article info:eu-repo/semantics/publishedVersion info:eu-repo/semantics/article |
| description | Epoxidation of a range of alkenes with aqueous H2O2 easily proceeds in the presence of the dititanium-containing 19-tungstodiarsenate(III) [Ti2(OH)2As2W19O67(H2O)]8– (1), which contains five-coordinate Ti atoms. The results of product and kinetics studies support a mechanism that involves a reversible interaction between H2O2 and the Ti–OH group of 1 to produce a titanium hydroperoxo complex followed by electrophilic oxygen atom transfer from the hydroperoxo ligand to the alkene substrate in the rate-limiting step. The effect of the alkene substrate nature has been investigated at the DFT level. A clear correlation between the energy of πC=C orbitals in the alkene and the turnover frequency values has been found, thereby indicating that the higher nucleophilicity of the alkene, the higher the reactivity. ONIOM (ONIOM = our own n-layered integrated molecular orbital and molecular mechanics) calculations have been employed to evaluate the role of steric effects of alkene substituents. The calculations show that the steric bulk can play a secondary role and tunes the activity in specific cases such as trans-stilbene. |
| eu_rights_str_mv | openAccess |
| format | article |
| id | LAURepo_4ad3a0094ed82a0ba656ab1c33b2b4bf |
| identifier_str_mv | 1434-1948 Donoeva, B. G., Trubitsina, T. A., Antonova, N. S., Carbó, J. J., Poblet, J. M., Al‐Kadamany, G., ... & Kholdeeva, O. A. (2010). Epoxidation of Alkenes with H 2 O 2 Catalyzed by Dititanium‐Containing 19‐Tungstodiarsenate (III): Experimental and Theoretical Studies. European Journal of Inorganic Chemistry, 2010(33), 5312-5317. |
| language_invalid_str_mv | en |
| network_acronym_str | LAURepo |
| network_name_str | Lebanese American University repository |
| oai_identifier_str | oai:laur.lau.edu.lb:10725/17247 |
| publishDate | 2010 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| spelling | Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical StudiesDonoeva, Baira G.Trubitsina, Tatiana A.Antonova, Nadya S.Carbo, Jorge J.Poblet, Josep M.Al-Kadamany, GhadaUlrich, KortzKortz, UlrichKholdeeva, Oxana A.Epoxidation of a range of alkenes with aqueous H2O2 easily proceeds in the presence of the dititanium-containing 19-tungstodiarsenate(III) [Ti2(OH)2As2W19O67(H2O)]8– (1), which contains five-coordinate Ti atoms. The results of product and kinetics studies support a mechanism that involves a reversible interaction between H2O2 and the Ti–OH group of 1 to produce a titanium hydroperoxo complex followed by electrophilic oxygen atom transfer from the hydroperoxo ligand to the alkene substrate in the rate-limiting step. The effect of the alkene substrate nature has been investigated at the DFT level. A clear correlation between the energy of πC=C orbitals in the alkene and the turnover frequency values has been found, thereby indicating that the higher nucleophilicity of the alkene, the higher the reactivity. ONIOM (ONIOM = our own n-layered integrated molecular orbital and molecular mechanics) calculations have been employed to evaluate the role of steric effects of alkene substituents. The calculations show that the steric bulk can play a secondary role and tunes the activity in specific cases such as trans-stilbene.Published2025-09-11T11:50:21Z2025-09-11T11:50:21Z20102010-10-15Articleinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article1434-1948http://hdl.handle.net/10725/17247https://doi.org/10.1002/ejic.201000615Donoeva, B. G., Trubitsina, T. A., Antonova, N. S., Carbó, J. J., Poblet, J. M., Al‐Kadamany, G., ... & Kholdeeva, O. A. (2010). Epoxidation of Alkenes with H 2 O 2 Catalyzed by Dititanium‐Containing 19‐Tungstodiarsenate (III): Experimental and Theoretical Studies. European Journal of Inorganic Chemistry, 2010(33), 5312-5317.http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.phphttps://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/ejic.201000615enEuropean Journal of Inorganic Chemistryinfo:eu-repo/semantics/openAccessoai:laur.lau.edu.lb:10725/172472025-10-23T14:10:30Z |
| spellingShingle | Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies Donoeva, Baira G. |
| status_str | publishedVersion |
| title | Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies |
| title_full | Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies |
| title_fullStr | Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies |
| title_full_unstemmed | Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies |
| title_short | Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies |
| title_sort | Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies |
| url | http://hdl.handle.net/10725/17247 https://doi.org/10.1002/ejic.201000615 http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.php https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/ejic.201000615 |