Hydrogenolysis of Polysilanes Catalyzed by Low-Valent Nickel Complexes
Bruno Pribanic
Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland
Search for more papers by this authorCorresponding Author
Monica Trincado
Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland
Search for more papers by this authorFrederik Eiler
Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland
Search for more papers by this authorMatthias Vogt
Universität Bremen, Fachbereich 2 Biologie/Chemie, Institut für Anorganische Chemie und Kristallographie, Leobenerstr. 7, 28359 Bremen, Germany
Search for more papers by this authorAleix Comas-Vives
Chemistry Department, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, 08193 Bellaterra, Catalonia, Spain
Search for more papers by this authorCorresponding Author
Hansjörg Grützmacher
Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland
Search for more papers by this authorBruno Pribanic
Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland
Search for more papers by this authorCorresponding Author
Monica Trincado
Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland
Search for more papers by this authorFrederik Eiler
Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland
Search for more papers by this authorMatthias Vogt
Universität Bremen, Fachbereich 2 Biologie/Chemie, Institut für Anorganische Chemie und Kristallographie, Leobenerstr. 7, 28359 Bremen, Germany
Search for more papers by this authorAleix Comas-Vives
Chemistry Department, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, 08193 Bellaterra, Catalonia, Spain
Search for more papers by this authorCorresponding Author
Hansjörg Grützmacher
Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland
Search for more papers by this authorDedicated to Professor José Manuel González Díaz on the occasion of his 60th birthday
Graphical Abstract
Si−Si bonds in polysilanes can be converted to Si−H bonds under mild conditions by using low-valent anionic Ni0 hydride catalysts. The reaction is reversible and dehydrogenative coupling of hydrosilanes is also possible. Experiments and DFT calculations indicate that low-coordinated 14- and 16-electron d10-Ni hydrides, silyl, and silane intermediates are involved in the catalytic cycle.
Abstract
The dehydrogenation of organosilanes (RxSiH4−x) under the formation of Si−Si bonds is an intensively investigated process leading to oligo- or polysilanes. The reverse reaction is little studied. To date, the hydrogenolysis of Si−Si bonds requires very harsh conditions and is very unselective, leading to multiple side products. Herein, we describe a new catalytic hydrogenation of oligo- and polysilanes that is highly selective and proceeds under mild conditions. New low-valent nickel hydride complexes are used as catalysts and secondary silanes, RR′SiH2, are obtained as products in high purity.
Conflict of interest
The authors declare no conflict of interest.
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