Controlled Growth of Dichlorogermanium Oligomers from Lewis Basic Hosts

Abstract

To branch or not to branch: A mild stepwise route to various linear and branched (GeCl2)x oligogermylenes supported by Lewis bases is reported, including the carbene‐bound Ge4 complex NHC⋅GeCl2Ge(GeCl3)2 (see picture). Dipp=2,6‐iPr2C6H3, NHC=N‐heterocyclic carbene.

Synthesis of a α-Chlorosilyl Functionalized Donor-Stabilized Chlorogermylene

“…Indeed, the reaction of 2 and 3 in a 1:1 ratio in toluene at room temperature afforded the NHC-stabilized (chlorosilyl)chlorogermylene 1 which was isolated as a crystalline compound (Scheme 2). We did not obtain any indication for the formation of donor-acceptor adducts between 2 and 3 or rearrangement products as often described for reactions of silylenes and germylenes [29,30]. Compound 1 was characterized in solution state by NMR spectroscopy as well as in solid state by single crystal X-ray molecular structure determination.…”

“…1 H and 13 C{ 1 H} NMR spectra were referenced to the peaks of residual protons of the deuterated solvent ( 1 H) or the deuterated solvent itself ( 13 C{ 1 H}). 29 Si{ 1 H} NMR spectra were referenced to external SiMe 4 .…”

IPr3Si3Cl5+: A Highly Reactive Cation with Silanide Character

“…Such insertion reactions similarly take place during the formation of Si(SiCl 3 ) 4 via the amine‐induced disproportionation of Si 2 Cl 6 and recently Rivard et al. described a comparable insertion reaction in germanium chemistry during the formation of (GeCl 3 ) 2 Ge–GeCl 2 –IDIPP …”

“…Such insertion reactions similarly take place during the formation of Si(SiCl 3 ) 4 via the amine-induced disproportionation of Si 2 Cl 6 [13] and recently Rivard et al described ac omparable insertionr eaction in germanium chemistry duringt he formation of (GeCl 3 ) 2 Ge-GeCl 2 -IDIPP. [18] All of the silicon atoms in 1 have different coordination numbers. Thereby,t he central silicon atom (Si2) with coordination number three exhibits ap yramidal environment( sum of bond angles3 09.938).…”

Halides of the Heavier Group 14 Homologues Germanium, Tin, and Lead—A Journey through Unusual Compounds and Oxidation States

“…This GeCl 2 ⋅dioxane complex is a common precursor for further substitution or reductive coupling reactions. Starting from IPr‐GeCl 2 (IPr=[(HCNDipp) 2 C]; Dipp=2,6‐ i Pr 2 C 6 H 3 ), Rivard and co‐workers developed a new synthetic bottom‐up method for the synthesis of oligomeric subhalides (GeCl 2 ) x ( x ≥2) in which GeCl 2 ⋅dioxane is added to give the branched polygermane IPr‐GeCl 2 ‐Ge(GeCl 3 ) 2 via the digermane IPr‐GeCl 2 ‐GeCl 2 (Scheme ) …”