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Efficient Catalytic Conversion of Dinitrogen to N(SiMe3)(3) Using a Homogeneous Mononuclear Cobalt Complex

TitleEfficient Catalytic Conversion of Dinitrogen to N(SiMe3)(3) Using a Homogeneous Mononuclear Cobalt Complex
Publication TypeJournal Article
Year of Publication2018
AuthorsSuzuki, T, Fujimoto, K, Takemoto, Y, Wasada-Tsutsui, Y, Ozawa, T, Inomata, T, Fryzuk, MD, Masuda, H
JournalACS CATALYSIS
Volume8
Pagination3011-3015
Date PublishedAPR
ISSN2155-5435
Abstract

Incorporation of the tridentate phosphine-enamidoiminophosphorane onto cobalt(II) produces tetrahedral Co(NpNPiPr)Cl, 1, which upon reduction under dinitrogen generates the T-shaped, paramagnetic Co(I) complex Co(NpNPiPr), 2. This paramagnetic T-shaped derivative is in equilibrium with the paramagnetic dinitrogen derivative Co(NpNPiPr)(N-2), 3, which can be detected by IR and low-temperature UV-vis spectroscopy. Both 1 and 2 act as homogeneous catalysts for the conversion of molecular nitrogen into tris(trimethylsilyl)amine (N(SiMe3)(3)) (similar to 200 equiv, quantified as NH4Cl after hydrolysis) in the presence of excess KC8 and Me3SiCl at low temperatures.

DOI10.1021/acscatal.7b04351