A Molybdenum(0) Isocyanide Analogue of [Ru(2,2'-Bipyridine)3]2+: Strong Reductant for Photoredox Catalysis

Büldt, Laura A. and Guo, Xingwei and Prescimone, Alessandro and Wenger, Oliver S.. (2016) A Molybdenum(0) Isocyanide Analogue of [Ru(2,2'-Bipyridine)3]2+: Strong Reductant for Photoredox Catalysis. Angewandte Chemie International Edition, 55 (37). pp. 11247-11250.

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We report the first homoleptic Mo0 complex with bidentate isocyanide ligands, which exhibits metal-to-ligand charge transfer (3MLCT) luminescence with quantum yields and lifetimes similar to Ru(bpy)32+ (bpy=2,2′-bipyridine). This Mo0 complex is a very strong photoreductant, which manifests in its capability to reduce acetophenone with essentially diffusion-limited kinetics as shown by time-resolved laser spectroscopy. The application potential of this complex for photoredox catalysis was demonstrated by the rearrangement of an acyl cyclopropane to a 2,3-dihydrofuran, which is a reaction that requires a reduction potential so negative that even the well-known and strongly reducing Ir(2-phenylpyridine)3 photosensitizer cannot catalyze it. Our study thus provides the proof-of-concept for the use of chelating isocyanides to obtain Mo0 complexes with long-lived 3MLCT excited states that are applicable to unusually challenging photoredox chemistry.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Wenger, Oliver and Büldt, Laura Allegra and Guo, Xingwei and Prescimone, Alessandro
Item Type:Article, refereed
Article Subtype:Research Article
Note:Publication type according to Uni Basel Research Database: Journal article -- The final publication is available at Wiley, see Doi link
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Last Modified:11 Jun 2018 09:02
Deposited On:11 Jan 2017 15:02

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