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Selective Photo-epoxidation of (R)-(+)- and (S)-(−)-Limonene by Chiral and Non-Chiral Dioxo-Mo(VI) Complexes Anchored on TiO2-Nanotubes

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Abstract

Selective epoxidation of the (R) and (S) isomers of limonene by dioxomolybdenum(VI) complexes anchored covalently on TiO2 nanotubes using UV–Vis light and O2 as the oxidizing agent was evaluated. It is interesting to study the effect of the ligands: bipyridine, terpyridine, and Schiff base on the stereoselective epoxidation of limonene through photostimulated oxygen atom transfer (OAT). OAT activity observed to increase in the following order: Mo(VI)O2(Schiff base)/TiO2-NT < Mo(VI)Cl2O2 (bipyridine)/TiO2-NT < Mo(VI)Cl2O2(terpyridine)/TiO2-NT. Moderate diastereoselectivity to the cis-isomer of complexes with “non-chiral” ligands like bipyridine and terpyridine was displayed. Contrary to the complex with the Schiff base as “chiral” ligand, it showed an increase in diastereoisomeric excess (52%), associated to an asymmetric double induction, assuming a complex metal-oxo sideway interaction with the trisubstituted olefins at the transition state.

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Data Availability

This work was presented to The 6th Latin-American Congress of Photocatalysis, Photochemistry and Photobiology LACP3, from 23 to 28 of September of 2019 at Bogota (https://www.utadeo.edu.co/en/lacp3-2019). The results are part of the thesis doctoral of HM but it is not realized public dissertation yet at the University of Industrial de Santander (https://www.uis.edu.co/webUIS/es/index.jsp).

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Acknowledgements

We gratefully recognize the financial support by the Universidad Industrial de Santander—UIS (Project 1868). H. M. author is grateful to COLCIENCIAS (Doctorados Nacionales 647 Program) for the scholarship program. The authors thank Parque Tecnológico Guatiguará-UIS by physicochemical characterization analyzes.

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  1. Centro de Investigaciones en Catálisis – CICAT, Escuela de Química, Universidad Industrial de Santander, Km. 2 vía El Refugio, Piedecuesta, Colombia

    Henry Martínez Q., Edgar A. Paez-Mozo & Fernando Martínez O.

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  1. Henry Martínez Q.
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  2. Edgar A. Paez-Mozo
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  3. Fernando Martínez O.
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Contributions

All authors contributed equally to this work. HM prepared, characterized the catalysts, and performed the photo-catalytic measurements and interpretation. EP and FM designed the experiments and contributed to the interpretation of the experimental results. All authors read and approved the final manuscript.

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Correspondence to Fernando Martínez O..

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Martínez Q., H., Paez-Mozo, E.A. & Martínez O., F. Selective Photo-epoxidation of (R)-(+)- and (S)-(−)-Limonene by Chiral and Non-Chiral Dioxo-Mo(VI) Complexes Anchored on TiO2-Nanotubes. Top Catal 64, 36–50 (2021). https://doi.org/10.1007/s11244-020-01355-3

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