3 years ago

Low Valent Magnesium Chemistry with a Superbulky ß‐Diketiminate Ligand

Sjoerd Harder, Thomas Xaver Gentner, Bastian Rösch, Gerd Ballmann, Jens Langer, Holger Elsen


The steric bulk of the well‐known DIPPBDI ligand (CH[C(CH3)N‐Dipp]2, DIPP =2,6‐diisopropylphenyl) was increased by replacing isopropyl for isopentyl groups. This very bulky DIPePBDI ligand could not stabilize the radical species (DIPePBDI)Mg•: reduction of (DIPePBDI)MgI with Na gave (DIPePBDI)2Mg2 with a rather long Mg‐Mg bond of 3.0513(8) Å. Addition of TMEDA prior to reduction gave mplex (DIPePBDI)2Mg2(C6H6) 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 (DIPePBDI)2Mg2(C6H6), which formally contains the anti‐aromatic anion C6H62‐, reacted with tBuOH as a Brønsted base to 1,3‐ and 1,4‐cyclohexadiene and with H2 as a two electron donor to (DIPePBDI)2Mg2H2 and C6H6. It also reductively cleaved the C‐F bond in fluorobenzene and gave (DIPePBDI)MgPh, (DIPePBDI)MgF and C6H6.

Publisher URL: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201812051

DOI: 10.1002/anie.201812051

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