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

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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.

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

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Publication details

The article was received on 12 Jun 2017, accepted on 17 Jul 2017 and first published on 26 Jul 2017


Article type: Paper
DOI: 10.1039/C7DT02136D
Citation: Dalton Trans., 2017, Advance Article
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    Bora-amidinate as a cooperative ligand in group 2 metal catalysis

    B. Freitag, C. A. Fischer, J. Penafiel, G. Ballmann, H. Elsen, C. Färber, D. F. Piesik and S. Harder, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT02136D

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