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REVIEW article

Front. Chem.

Sec. Catalytic Reactions and Chemistry

Coordinating ability and versatility of organosulfur-based ligands in transition metal catalyzed hydrogenative and hydrogen auto-transfer processes

  • 1. University of Turin, Turin, Italy

  • 2. Cube Labs, Rome, Italy

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Abstract

Transition metal complexes with sulfur-donor ligands serve as efficient catalysts in numerous homogeneous reactions, owing to the coordination diversity of sulfur-based ligands and the possibility to obtain chiral and achiral complexes. Historically dominated by phosphorus and nitrogen, transition metal compounds with electron-rich sulfur-donor ligands have recently attracted research interest because of their close connection with enzymatic transformation. This review presents a comprehensive overview of recent applications of sulfur-ligated metal complexes in hydrogenative and strictly related hydrogen auto-transfer processes, namely hydrogenation, transfer hydrogenation and borrowing hydrogen reactions. Particular attention is given to the impact of ligand selection on the reaction outcomes, and on the influence of sulfur to give stability at the catalytically active metal complex. Additionally, the review compares conventional hydrogenation and transfer hydrogenation strategies with emerging approaches involving metal-ligand cooperation in the presence of sulfur-based ligands.

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Keywords

Borrowing hydrogen, homogeneous catalysis, Hydrogenation, sulfur-based ligands, transfer hydrogenation

Received

14 November 2025

Accepted

29 December 2025

Copyright

© 2025 Paraschiv, Brambilla, Prandi, Cravotto, Baldino and Martina. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) or licensor are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.

*Correspondence: Salvatore Baldino; Katia Martina

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All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article or claim that may be made by its manufacturer is not guaranteed or endorsed by the publisher.

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