Water co-catalysis in aerobic olefin epoxidation mediated by ruthenium oxo complexes

Qun Cao; Martin Diefenbach; Calum Maguire; Vera Krewald; Mark J. Muldoon; Ulrich Hintermair

doi:10.1039/d3sc05516g

Water co-catalysis in aerobic olefin epoxidation mediated by ruthenium oxo complexes

Qun Cao, Martin Diefenbach, Calum Maguire, Vera Krewald, Mark J. Muldoon, Ulrich Hintermair

Research output: Contribution to journal › Article › peer-review

1 Citation (SciVal)

Abstract

We report the development of a versatile Ru-porphyrin catalyst system which performs the aerobic epoxidation of aromatic and aliphatic (internal) alkenes under mild conditions, with product yields of up to 95% and turnover numbers (TON) up to 300. Water is shown to play a crucial role in the reaction, significantly increasing catalyst efficiency and substrate scope. Detailed mechanistic investigations employing both computational studies and a range of experimental techniques revealed that water activates the Ru^VI di-oxo complex for alkene epoxidation via hydrogen bonding, stabilises the Ru^IV mono-oxo intermediate, and is involved in the regeneration of the Ru^VI di-oxo complex leading to oxygen atom exchange. Distinct kinetics are obtained in the presence of water, and side reactions involved in catalyst deactivation have been identified.

Original language	English
Journal	Chemical Science
Early online date	9 Jan 2024
DOIs	https://doi.org/10.1039/d3sc05516g
Publication status	Published - 9 Jan 2024

Bibliographical note

Data availability: The datasets supporting this article have been uploaded as part of the ESI

Funding

This work was supported by the EPSRC through the UK Catalysis Hub (EP/R027129/1), the Dynamic Reaction Monitoring Facility at the University of Bath (EP/P001475/1), and the Royal Society (UF160458; fellowship to UH). We thank John Lowe, Catherine Lyall and Shaun Reeksting from the University of Bath for help and assistance with NMR, UV-Vis and MS analyses, and John Andrews and Paul Dallin from Clairet Scientific for help with Raman spectroscopy. Part of the calculations were performed on the Lichtenberg high-performance computer of the Technische Universität Darmstadt. VK and MD thank the Hessian Competence Center for High Performance Computing funded by the Hessen State Ministry of Higher Education, Research and the Arts for support.

Funders	Funder number
Engineering and Physical Sciences Research Council
Royal Society	UF160458
Hessisches Ministerium für Wissenschaft und Kunst
UK Catalysis Hub	EP/P001475/1, EP/R027129/1

ASJC Scopus subject areas

General Chemistry

Access to Document

10.1039/d3sc05516gLicence: CC BY

Cite this

@article{6d922f69bfba47759802b8ad9e06b7ae,

title = "Water co-catalysis in aerobic olefin epoxidation mediated by ruthenium oxo complexes",

abstract = "We report the development of a versatile Ru-porphyrin catalyst system which performs the aerobic epoxidation of aromatic and aliphatic (internal) alkenes under mild conditions, with product yields of up to 95% and turnover numbers (TON) up to 300. Water is shown to play a crucial role in the reaction, significantly increasing catalyst efficiency and substrate scope. Detailed mechanistic investigations employing both computational studies and a range of experimental techniques revealed that water activates the RuVI di-oxo complex for alkene epoxidation via hydrogen bonding, stabilises the RuIV mono-oxo intermediate, and is involved in the regeneration of the RuVI di-oxo complex leading to oxygen atom exchange. Distinct kinetics are obtained in the presence of water, and side reactions involved in catalyst deactivation have been identified.",

author = "Qun Cao and Martin Diefenbach and Calum Maguire and Vera Krewald and Muldoon, {Mark J.} and Ulrich Hintermair",

note = "Data availability: The datasets supporting this article have been uploaded as part of the ESI",

year = "2024",

month = jan,

day = "9",

doi = "10.1039/d3sc05516g",

language = "English",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

}

TY - JOUR

T1 - Water co-catalysis in aerobic olefin epoxidation mediated by ruthenium oxo complexes

AU - Cao, Qun

AU - Diefenbach, Martin

AU - Maguire, Calum

AU - Krewald, Vera

AU - Muldoon, Mark J.

AU - Hintermair, Ulrich

N1 - Data availability: The datasets supporting this article have been uploaded as part of the ESI

PY - 2024/1/9

Y1 - 2024/1/9

N2 - We report the development of a versatile Ru-porphyrin catalyst system which performs the aerobic epoxidation of aromatic and aliphatic (internal) alkenes under mild conditions, with product yields of up to 95% and turnover numbers (TON) up to 300. Water is shown to play a crucial role in the reaction, significantly increasing catalyst efficiency and substrate scope. Detailed mechanistic investigations employing both computational studies and a range of experimental techniques revealed that water activates the RuVI di-oxo complex for alkene epoxidation via hydrogen bonding, stabilises the RuIV mono-oxo intermediate, and is involved in the regeneration of the RuVI di-oxo complex leading to oxygen atom exchange. Distinct kinetics are obtained in the presence of water, and side reactions involved in catalyst deactivation have been identified.

AB - We report the development of a versatile Ru-porphyrin catalyst system which performs the aerobic epoxidation of aromatic and aliphatic (internal) alkenes under mild conditions, with product yields of up to 95% and turnover numbers (TON) up to 300. Water is shown to play a crucial role in the reaction, significantly increasing catalyst efficiency and substrate scope. Detailed mechanistic investigations employing both computational studies and a range of experimental techniques revealed that water activates the RuVI di-oxo complex for alkene epoxidation via hydrogen bonding, stabilises the RuIV mono-oxo intermediate, and is involved in the regeneration of the RuVI di-oxo complex leading to oxygen atom exchange. Distinct kinetics are obtained in the presence of water, and side reactions involved in catalyst deactivation have been identified.

UR - http://www.scopus.com/inward/record.url?scp=85182930598&partnerID=8YFLogxK

U2 - 10.1039/d3sc05516g

DO - 10.1039/d3sc05516g

M3 - Article

AN - SCOPUS:85182930598

SN - 2041-6520

JO - Chemical Science

JF - Chemical Science

ER -

Water co-catalysis in aerobic olefin epoxidation mediated by ruthenium oxo complexes

Abstract

Bibliographical note

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

AP19: Developing Catalyst Strategies for a Truly Circular Plastic Economy

Cite this

Water co-catalysis in aerobic olefin epoxidation mediated by ruthenium oxo complexes

Abstract

Bibliographical note

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Projects

AP19: Developing Catalyst Strategies for a Truly Circular Plastic Economy

Cite this