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://dx.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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