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Unravelling the reaction mechanism for the Claisen–Tishchenko condensation catalysed by Mn(I)-PNN complexes: a DFT study

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Abstract

In this work, we study the potential catalytic role of previously identified Mn(I)-PNN complexes in the Claisen–Tishchenko reaction. An in-depth investigation of the reaction mechanism suggests that, after activation of the 16e pre-catalyst, a hydrogenated 18e active species is generated. Based on calculations, rate-limiting barriers in a range of ca. 15–20 kcal mol−1 are seen for a model process consisting in the esterification of acetaldehyde into ethyl acetate at 100 °C and 1 atm reaction conditions (in toluene solution). Our hypothesis is centred on the role of the Mn centre as the only active site involved in both elementary steps, namely hydride borrowing and C–O bond formation. During this C–O bond formation step, diastereoisomers (RN,R) and (RN,S) [or their enantiomeric pairs (SN,S) and (SN,R)] can be generated, with calculations showing a preference towards the (RN,R) pathway.

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Acknowledgements

This research has been supported by the King Abdullah University of Science and Technology (KAUST). Gratitude is also due to the KAUST Supercomputing Laboratory using the supercomputer Shaheen II for providing the computational resources. LMA is an ULPGC Postdoc Fellow, and thanks Universidad de Las Palmas de Gran Canaria (ULPGC). LMA also acknowledges the Scientific Committee of ESPA 2018 Conference for selecting him as speaker.

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Authors and Affiliations

  1. CIDIA-FEAM (Unidad Asociada al Consejo Superior de Investigaciones Científicas, CSIC, avalada por el Instituto de Ciencia de Materiales de Sevilla, Universidad de Sevilla), Instituto de Estudios Ambientales y Recursos Naturales (i-UNAT), Universidad de Las Palmas de Gran Canaria (ULPGC), Campus de Tafira, 35017, Las Palmas de Gran Canaria, Spain

    Luis Miguel Azofra

  2. Departamento de Química, Universidad de Las Palmas de Gran Canaria (ULPGC), Campus de Tafira, 35017, Las Palmas de Gran Canaria, Spain

    Luis Miguel Azofra

  3. KAUST Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia

    Luigi Cavallo

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  1. Luis Miguel Azofra
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  2. Luigi Cavallo
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Correspondence to Luis Miguel Azofra or Luigi Cavallo.

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Dedicated to Prof. Dr. Otilia Mó and Prof. Dr. Manuel Yáñez on occasion of their 70th birthdays.

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Published as part of the special collection of articles derived from the 11th Congress on Electronic Structure: Principles and Applications (ESPA-2018).

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Azofra, L.M., Cavallo, L. Unravelling the reaction mechanism for the Claisen–Tishchenko condensation catalysed by Mn(I)-PNN complexes: a DFT study. Theor Chem Acc 138, 64 (2019). https://doi.org/10.1007/s00214-019-2449-7

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