Yttrium-Catalyzed Amine鈥揝ilane Dehydrocoupling: Extended Reaction Scope with a Phosphorus-Based Ligand

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• 作者：Adi E. Nako ; Wenyi Chen ; Andrew J. P. White ; Mark R. Crimmin
• 刊名：Organometallics
• 出版年：2015
• 出版时间：September 14, 2015
• 年：2015
• 卷：34
• 期：17
• 页码：4369-4375
• 全文大小：435K
• ISSN：1520-6041

文摘

The scope of the catalytic dehydrocoupling of primary and secondary amines with phenylsilanes has been investigated using [Y{N(SiMe₃)₂}₃] and a four-coordinate analogue bearing a cyclometalated phosphonium methylide ligand. Inclusion of the phosphorus-based ligand on yttrium results in increased substrate scope in comparison to the tris(amide) analogue. While reversible C鈥揌 bond activation of the cyclometalated ligand was observed in stoichiometric experiments, D-labeling experiments and DFT calculations suggest that reversible ligand activation is not involved in silazane formation under catalytic conditions. We suggest that the extended reaction scope with the four-coordinate yttrium phosphonium methylide complex relative to the three-coordinate yttrium (tris)amide complex is a result of differences in the ease of amine inhibition of catalysis.