Isopropyl

Adduct

Ligand (biochemistry)

Medicinal chemistry

Receptor

Organic chemistry

Chemistry

Steric effects

Fluorobenzene

Benzene

Magnesium

Biochemistry

Stereochemistry

Angewandte Chemie International Edition

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 t BuOH 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 .

Low Valent Magnesium Chemistry with a Super Bulky β‐Diketiminate Ligand