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Isolation of Catalytic Intermediates in Hydroamination Reactions: Insertion of Internal Alkynes into a Zirconium–Amido Bond


  • We gratefully acknowledge Boehringer Ingelheim (Canada) Ltd. and the NSERC for financially supporting this work. D.C.L. thanks NSERC for a CGSD scholarship. We thank N. Yonson for assistance with X-ray crystallography.


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Insert alkyne to continue: Reaction of a bis(ureate) zirconium dimethylamido complex with electron-rich alkynes leads to vinylamine insertion products (see scheme). The insertion of C[BOND]C unsaturated bonds into M[BOND]N bonds is proposed as a key step in lanthanide chemistry and, more recently, hydroamination reactions catalyzed by Group 4 metals. For the first time, these elusive intermediates have been isolated and characterized on a catalytically active d0-metal center.