A Neutral, Monomeric Germanium(I) Radical

Abstract

Stoichiometric reduction of the bulky β-diketiminato germanium(II) chloride complex [((But)Nacnac)GeCl] ((But)Nacnac = [{N(Dip)C(Bu(t))}(2)CH](-), Dip = C(6)H(3)Pr(i)(2)-2,6) with either sodium naphthalenide or the magnesium(I) dimer [{((Mes)Nacnac)Mg}(2)] ((Mes)Nacnac = [(MesNCMe)(2)CH](-), Mes = mesityl) afforded the radical complex [((But)Nacnac)Ge:](•) in moderate yields. X-ray crystallographic, EPR/ENDOR spectroscopic, computational, and reactivity studies revealed this to be the first authenticated monomeric, neutral germanium(I) radical.

Mechanistic studies of CO2 reduction to methanol mediated by an N-heterocyclic germylene hydride

“…In both cases the only isolated products are diamido germylene complexes with 1,3-hydride migration to the backbone of the ligands. 11b, 13 However, compound 1 cannot activate CO 2 even at elevated temperatures in toluene or benzene.…”

On the non-innocence of “Nacnacs”: ligand-based reactivity in β-diketiminate supported coordination compounds

“…[69][70][71] However, subtle changes in the steric profile of the BDI ligand or the choice of the reducing agent have very marked and unpredictable effects on the course of these reductions. 72 Reducing the steric profile of the BDI ligand by replacing the Dipp N-substituents by Mes groups destabilizes the Ge(I) radical and promotes BDI Mes,tBu reductive cleavage. 72 Reducing the steric profile of the BDI ligand by replacing the Dipp N-substituents by Mes groups destabilizes the Ge(I) radical and promotes BDI Mes,tBu reductive cleavage.…”

“…72 Instead, Jones and co-workers observed hydride migration to the BDI β-carbon (Scheme 50), yielding the diamido germylene product whose structure is reproduced in Fig. 72 Instead, Jones and co-workers observed hydride migration to the BDI β-carbon (Scheme 50), yielding the diamido germylene product whose structure is reproduced in Fig.…”

Germanium-centered free radicals studied by muon spin spectroscopy

“…[1][2][3][4] Germanium-centered radicals are far more reactive, and are therefore generally observed only at low temperatures or as transient species. 5,6 Several examples of stable organogermanium radicals have been reported in which the germanium radical center is protected by great steric hindrance.…”