Issue 2, 2021

Cooperative activating effects of metal ion and Brønsted acid on a metal oxo species

Abstract

Metal oxo (M[double bond, length as m-dash]O) complexes are common oxidants in chemical and biological systems. The use of Lewis acids to activate metal oxo species has attracted great interest in recent years, especially after the discovery of the CaMn4O5 cluster in the oxygen-evolving centre of photosystem II. Strong Lewis acids such as Sc3+ and BF3, as well as strong Brønsted acids such as H2SO4 and CF3SO3H, are commonly used to activate metal oxo species. In this work, we demonstrate that relatively weak Lewis acids such as Ca2+ and other group 2 metal ions, as well as weak Brønsted acids such as CH3CO2H, can readily activate the stable RuO4 complex towards the oxidation of alkanes. Notably, the use of Ca2+ and CH3CO2H together produces a remarkable cooperative effect on RuO4, resulting in a much more efficient oxidant. DFT calculations show that Ca2+ and CH3CO2H can bind to two oxo ligands to form a chelate ring. This results in substantial lowering of the barrier for hydrogen atom abstraction from cyclohexane.

Graphical abstract: Cooperative activating effects of metal ion and Brønsted acid on a metal oxo species

Supplementary files

Article information

Article type
Edge Article
Submitted
27 Jūl. 2020
Accepted
20 Okt. 2020
First published
21 Okt. 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 632-638

Cooperative activating effects of metal ion and Brønsted acid on a metal oxo species

G. Chen, L. Ma, P. Lo, C. Mak, K. Lau and T. Lau, Chem. Sci., 2021, 12, 632 DOI: 10.1039/D0SC04069J

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements