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Bora-amidinate as a cooperative ligand in group 2 metal catalysis.
Syntheses and crystal structures of the monomeric bora-amidinate (bam) complexesDIPP NBN-Mg·(THF)3 andDIPP NBN-Ca·(THF)4 are presented;DIPP NBN = HB[N(2,6-iPr2 -C6 H3 )]2 . The simplicity of their1 H NMR spectra in THF-d8 suggest that their monomeric solid state structures are retained in solution.DIPP NBN-Mg·(THF)3 in C6 D6 , however, is in equilibrium with a dimeric species. Calculations (B3PW91/6-311++G**) reveal a very high localized negative charge (NPA: -1.103) on the N atoms inDIPP NBN-Mg. The strongly basic properties of the bam ligand are in agreement with catalytic activity of these complexes in the intramolecular alkene hydroamination. A mechanism is proposed in which the bam ligand is non-innocent and cooperative, playing an active role in substrate deprotonation and product protonation.
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