Inorganic Chemistry, Vol.59, No.18, 13473-13480, 2020
Nickel(0)-Induced beta-H Elimination of Magnesium Alkyls: Formation and Reactivity of Heterometallic Hydrides
We report the synthesis and reactivity of heterometallic Mg-Ni complexes with bridging hydrides. Treatment of magnesium monoalkyl complexes, which are supported by a tridentate beta-diketiminato ligand bearing a pendent phosphine group, with nickel(0) reagent Ni(COD)(2) (COD: 1,5-cyclooctadiene) at a molar ratio of 2:1 resulted in the formation of a heterotrimetallic hydride-bridged [Mg-Ni-Mg] complex via facile elimination of the corresponding alkenes. A heterobimetallic hydride-bridged [Mg-Ni] complex served as an intermediate species for the formation of the [Mg-Ni-Mg] complex. Computational studies revealed that the reaction was initiated by coordination of nickel to magnesium followed by an alkyl group transfer. beta-H elimination at the nickel center subsequently occurred to give the heterometallic hydride-bridged complex. Density functional theory analysis also highlighted a three-center two-electron interaction for the Mg-H-Ni unit. The hydride-bridged [Mg-Ni-Mg] complex showed diverse reactivity toward unsaturated small molecules. For instance, reactions with isocyanides provided heterometallic species by coordination of isocyanides to the nickel center, with no subsequent reduction detected. Isocyanides could also be dissociated at 80 degrees C. In contrast, hydromagnesiation occurred upon treatment of the heterotrimetallic hydride with carbodiimides, affording C-3-symmetric complexes with three heteroleptic magnesium mixed beta-diketiminate/amidinate moieties. The hydride-bridged heterotrimetallic complex underwent dehydrogenation reaction with phenyl acetylene to produce an acetylide-bridged [Mg-Ni-Mg] complex.