Bora-amidinate as a cooperative ligand in group 2 metal catalysis

Abstract

Syntheses and crystal structures of the monomeric bora-amidinate (bam) complexes ^DIPPNBN-Mg·(THF)₃ and ^DIPPNBN-Ca·(THF)₄ are presented; ^DIPPNBN = HB[N(2,6-iPr₂-C₆H₃)]₂. The simplicity of their ¹H NMR spectra in THF-d₈ suggest that their monomeric solid state structures are retained in solution. ^DIPPNBN-Mg·(THF)₃ in C₆D₆, 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 in ^DIPPNBN-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.