A Digermyne with a Ge–Ge Single Bond That Activates Dihydrogen in the Solid State

Abstract

The reduction of the bulky amido-germanium(II) chloride complex, LGeCl (L = N(SiMe(3))(Ar*); Ar* = C(6)H(2)Me{C(H)Ph(2)}(2)-4,2,6), with the magnesium(I) dimer, [{((Mes)Nacnac)Mg}(2)] ((Mes)Nacnac = [(MesNCMe)(2)CH](-); Mes = mesityl), afforded LGeGeL, which represents the first example of a digermyne with a Ge-Ge single bond. Computational studies of the compound have highlighted significant electronic differences between it and multiply bonded digermynes. LGeGeL was shown to cleanly activate H(2) in solution or the solid state, at temperatures as low as -10 °C, to give the mixed valence compound, LGeGe(H)(2)L.

Weak Arene Stabilization of Bulky Amido‐Germanium(II) and Tin(II) Monocations

“…ÀN(Ar*)(SiMe 3 ), Ar* = C 6 H 2 {C(H)Ph 2 } 2 Me-2,6,4), which we believed might be suitable for this task. [14] Moreover, we have utilized these amides in the preparation of the first monomeric amido Group 14 metal(II) halide complexes (e.g. LECl, E = Ge or Sn), which we saw as ideal precursors for the synthesis of the cations, LE + , by halide abstraction methods.…”

Reaction Mechanism of the Symmetry‐Forbidden [2+2] Addition of Ethylene and Acetylene to Amido‐Substituted Digermynes and Distannynes Ph2NEENPh2, (E=Ge, Sn): A Theoretical Study

“…reported that the amido substituted digermyne L*GeGeL* with bulky substituents (L* =ÀN(Ar*)(SiMe 3 ); Ar* = C 6 H 2 Me{C(H)Ph 2 } 2 -4,2,6) possesses aG e ÀGe single bond, which is quite long (2.709 ). [11] Inspection of the electronic structure showedt hat there is significant N!Ge p donation resulting in ap artial N=Ge p bond, which prevents the formation of aG eGe multiple bond. [11] Interestingly,t he employmento fa ne ven 2,6) gives aG e-Ge multiple bond, whichi s much shorter (2.357 ) than in L*GeGeL*.…”

“…[11] Inspection of the electronic structure showedt hat there is significant N!Ge p donation resulting in ap artial N=Ge p bond, which prevents the formation of aG eGe multiple bond. [11] Interestingly,t he employmento fa ne ven 2,6) gives aG e-Ge multiple bond, whichi s much shorter (2.357 ) than in L*GeGeL*. [12] The more bulky substituents L + induce ar otationa bout the NÀGe bond due to steric repulsion, whichr educes the N!Ge p donation.…”

“…Both amido-digermynes L*GeGeL* and L + GeGeL + rapidly react with H 2 in solution and in the solid state at low temperaturesu pt o À10 8C. [11,12] Thus, diamido substituted digermynesare more reactive than the aryl digermynesA r 'GeGeAr'. [7] Calculations showedt hat amido-digermynes have very small HOMO-LUMO gaps (< 0.8 eV), [12] which is much smaller than the model arylalkyne analogues (ca.…”

Synthesis, Reactivity, and Computational Analysis of Halophosphines Supported by Dianionic Guanidinate Ligands

“…1 Several years later he also showed the addition of dihydrogen to distannynes to give tin(II) hydrides. [2][3][4][5][6][7][8] A notable surge in the reported reactivity of "frustrated Lewis pairs" (FLP) was kickstarted by Stephan et al, where they reported metalfree reversible hydrogen activation by the unquenched reactivity of a phosphine-borane ((C6H2Me3)2P(C6F4)B(C6F5)2), which features a Lewis acidic boron and Lewis basic phosphorus. 9 Since then, many different FLP systems have been developed 10 and reactivity with a variety of substrates has been observed, including B-H bonds, 11 CO2, 12,13 unsaturated bonds 10 and even catalytic, metal-free hydrogenation.…”