Low Valent Magnesium Chemistry with a Super Bulky β-Diketiminate Ligand
Gentner T, Rösch B, Ballmann G, Langer J, Elsen H, Harder S (2019)
Publication Type: Journal article
Publication year: 2019
Journal
Book Volume: 58
Pages Range: 607-611
Journal Issue: 2
DOI: 10.1002/anie.201812051
Abstract
The steric bulk of the well-known DIPP BDI ligand (CH[C(CH 3 )N-DIPP] 2 , DIPP=2,6-diisopropylphenyl) was increased by replacing isopropyl for isopentyl groups. This very bulky DIPeP BDI ligand could not stabilize the radical species ( DIPeP BDI)Mg . : reduction of ( DIPeP BDI)MgI with Na gave ( DIPeP BDI) 2 Mg 2 with a rather long Mg-Mg bond of 3.0513(8) Å. Addition of TMEDA prior to reduction gave complex ( DIPeP BDI) 2 Mg 2 (C 6 H 6 ), which could also be obtained as its THF adduct. It is speculated that combination of a bulky spectator ligand and TMEDA prevents dimerization of the intermediate Mg I radical, which then reacts with the benzene solvent. Complex ( DIPeP BDI) 2 Mg 2 (C 6 H 6 ), which formally contains the anti-aromatic anion C 6 H 6 2− , reacted with tBuOH as a Brønsted base to 1,3- and 1,4-cyclohexadiene and with H 2 as a two electron donor to ( DIPeP BDI) 2 Mg 2 H 2 and C 6 H 6 . It also reductively cleaved the C−F bond in fluorobenzene and gave ( DIPeP BDI)MgPh, ( DIPeP BDI)MgF, and C 6 H 6 .
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How to cite
APA:
Gentner, T., Rösch, B., Ballmann, G., Langer, J., Elsen, H., & Harder, S. (2019). Low Valent Magnesium Chemistry with a Super Bulky β-Diketiminate Ligand. Angewandte Chemie International Edition, 58(2), 607-611. https://doi.org/10.1002/anie.201812051
MLA:
Gentner, Thomas, et al. "Low Valent Magnesium Chemistry with a Super Bulky β-Diketiminate Ligand." Angewandte Chemie International Edition 58.2 (2019): 607-611.
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