Carboxylate and coordination influence on the formation of an active RuV Oxo species

Abstract Understanding the structure of Ru(V)-oxo species is crucial for designing novel catalysts for sustainable energy applications, such as water splitting for green hydrogen production. This study reports the EPR detection of a Ru(V)-oxo intermediate stabilized by terpyridine and phenanthroline...

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Main Authors: Jamal El-Abid, Kevin M. Dorst, Andrew K. Inge, Oscar Verho, Varun Kundi, Priyank V. Kumar, Anders Thapper, Biswanath Das
Format: Article
Language:English
Published: Nature Portfolio 2025-02-01
Series:Scientific Reports
Online Access:https://doi.org/10.1038/s41598-025-89062-5
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author Jamal El-Abid
Kevin M. Dorst
Andrew K. Inge
Oscar Verho
Varun Kundi
Priyank V. Kumar
Anders Thapper
Biswanath Das
author_facet Jamal El-Abid
Kevin M. Dorst
Andrew K. Inge
Oscar Verho
Varun Kundi
Priyank V. Kumar
Anders Thapper
Biswanath Das
author_sort Jamal El-Abid
collection DOAJ
description Abstract Understanding the structure of Ru(V)-oxo species is crucial for designing novel catalysts for sustainable energy applications, such as water splitting for green hydrogen production. This study reports the EPR detection of a Ru(V)-oxo intermediate stabilized by terpyridine and phenanthroline carboxylate ligands. The interaction between the carboxylate group and the ruthenium center, along with PCET-dependent hemilability under oxidative conditions, plays a critical role in achieving the high-valent state. Subtle changes in the coordination environment around the central metal also proved to be essential. Low-temperature NMR, high-resolution mass spectrometry, UV–Vis spectroscopy, and density functional theory calculations support these findings.
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spelling doaj-art-e95a12e9d3c340e68f0f67f571bc8ee92025-08-20T03:10:55ZengNature PortfolioScientific Reports2045-23222025-02-011511810.1038/s41598-025-89062-5Carboxylate and coordination influence on the formation of an active RuV Oxo speciesJamal El-Abid0Kevin M. Dorst1Andrew K. Inge2Oscar Verho3Varun Kundi4Priyank V. Kumar5Anders Thapper6Biswanath Das7Department of Organic Chemistry, Arrhenius Laboratory Stockholm UniversityDepartment of Organic Chemistry, Arrhenius Laboratory Stockholm UniversityDepartment of Materials and Environmental Chemistry, Stockholm UniversityDepartment of Medicinal Chemistry, Biomedicinskt Centrum BMC, Uppsala UniversitySchool of Chemical Engineering, The University of New South WalesSchool of Chemical Engineering, The University of New South WalesDepartment of Chemistry–Ångström Laboratory, Uppsala UniversityDepartment of Organic Chemistry, Arrhenius Laboratory Stockholm UniversityAbstract Understanding the structure of Ru(V)-oxo species is crucial for designing novel catalysts for sustainable energy applications, such as water splitting for green hydrogen production. This study reports the EPR detection of a Ru(V)-oxo intermediate stabilized by terpyridine and phenanthroline carboxylate ligands. The interaction between the carboxylate group and the ruthenium center, along with PCET-dependent hemilability under oxidative conditions, plays a critical role in achieving the high-valent state. Subtle changes in the coordination environment around the central metal also proved to be essential. Low-temperature NMR, high-resolution mass spectrometry, UV–Vis spectroscopy, and density functional theory calculations support these findings.https://doi.org/10.1038/s41598-025-89062-5
spellingShingle Jamal El-Abid
Kevin M. Dorst
Andrew K. Inge
Oscar Verho
Varun Kundi
Priyank V. Kumar
Anders Thapper
Biswanath Das
Carboxylate and coordination influence on the formation of an active RuV Oxo species
Scientific Reports
title Carboxylate and coordination influence on the formation of an active RuV Oxo species
title_full Carboxylate and coordination influence on the formation of an active RuV Oxo species
title_fullStr Carboxylate and coordination influence on the formation of an active RuV Oxo species
title_full_unstemmed Carboxylate and coordination influence on the formation of an active RuV Oxo species
title_short Carboxylate and coordination influence on the formation of an active RuV Oxo species
title_sort carboxylate and coordination influence on the formation of an active ruv oxo species
url https://doi.org/10.1038/s41598-025-89062-5
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