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Open AccessArticle

Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(Triphenylphosphine)Cobalt(I)

Van’t Hoff Institute for Molecular Sciences (HIMS), Homogeneous, Supramolecular and Bio-Inspired Catalysis, Universiteit van Amsterdam, P.O. Box 94720, 1090 GS Amsterdam, The Netherlands
Academic Editors: Duncan H. Gregory and Gianfranco Pacchioni
Inorganics 2016, 4(3), 21;
Received: 14 April 2016 / Revised: 23 June 2016 / Accepted: 28 June 2016 / Published: 5 July 2016
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
Recently, homogeneous cobalt systems were reported to catalyze the reductive silylation of dinitrogen. In this study the investigations on the silylation of dinitrogen catalyzed by CoH(PPh3)3N2 are presented. We show that in the presence of the title compound, the reaction of N2 with trimethylsilylchloride and sodium yields, on average, 6.7 equivalents of tris(trimethylsilyl)amine per Co atom in THF (tetrahydrofuran). The aim was to elucidate whether the active catalyst is: (a) the [Co(PPh3)3N2] anion formed after two-electron reduction of the title compound; or (b) a species formed via decomposition of CoH(PPh3)3N2 in the presence of the highly reactive substrates. Time profile, and IR and EPR spectroscopic investigations show instability of the pre-catalyst under the applied conditions which suggests that the catalytically active species is formed through in situ modification of the pre-catalyst. View Full-Text
Keywords: nitrogen activation; silylamines; cobalt; homogeneous catalysis nitrogen activation; silylamines; cobalt; homogeneous catalysis
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MDPI and ACS Style

Dzik, W.I. Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(Triphenylphosphine)Cobalt(I). Inorganics 2016, 4, 21.

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