Dithienylethene-based photoswitchable phosphines for palladium-catalyzed Stille coupling reaction
Sherstiuk, Anastasiia (Universitat Autònoma de Barcelona. Departament de Química)
Lledós, Agustí (Universitat Autònoma de Barcelona. Departament de Química)
Lönnecke, Peter (Leipzig University. Institute of Inorganic Chemistry)
Hernando Campos, Jordi (Universitat Autònoma de Barcelona. Departament de Química)
Sebastián Pérez, Rosa Maria (Universitat Autònoma de Barcelona. Departament de Química)
Hey-Hawkins, Evamarie (Leipzig University. Institute of Inorganic Chemistry)

Date:	2024
Abstract:	Homogeneous transition metal catalysis is a constantly developing field in chemical sciences. A growing interest in this area is photoswitchable catalysis, which pursues in situ modulation of catalyst activity through noninvasive light irradiation. Phosphorus ligands are excellent targets to accomplish this goal by introducing photoswitchable moieties; however, only a limited number of examples have been reported so far. In this work, we have developed a series of palladium complexes capable of catalyzing the Stille coupling reaction that contain photoisomerizable phosphine ligands based on dithienylethene switches. Incorporation of electron-withdrawing substituents into these dithienylethene moieties allows variation of the electron density on the phosphorus atom of the ligands upon light irradiation, which in turn leads to a modulation of the catalytic properties of the formed complexes and their activity in a model Stille coupling reaction. These results are supported by theoretical computations, which show that the energy barriers for the rate-determining steps of the catalytic cycle decrease when the photoswitchable phosphine ligands are converted to their closed state.
Grants:	European Commission 860322 Agència de Gestió d'Ajuts Universitaris i de Recerca 2021/SGR-00064
Note:	Altres ajuts: acords transformatius de la UAB
Rights:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Language:	Anglès
Document:	Article ; recerca ; Versió publicada
Subject:	Dithienylethenes ; Phosphines ; Catalysis ; Photoswitch
Published in:	Inorganic Chemistry, (April 2024) , ISSN 0020-1669

DOI: 10.1021/acs.inorgchem.3c04423
PMID: 38624066

13 p, 3.5 MB

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Research literature > UAB research groups literature > Research Centres and Groups (research output) > Experimental sciences > Group in Electrochemistry, Photochemistry and Organic Reactivity (GEFRO)
Articles > Research articles
Articles > Published articles