Development of a Library of Extremely Bulky Amide Ligands, and their use for the Stabilization of Germanium(I) and Germanium(II) Compounds

Palak Garg, Deepak Dange, Cameron Jones

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Eleven new extremely bulky aryl/silyl substituted secondary amines, L1–11H, have been prepared. These incorporate a combination of one of the bulky aryl groups, C6H2{C(H)Ph2}2R-2,6,4; R=Me (Ar*), Pri (Ar); C6H2{C(H)(C6H3But2-3,5)2}2Me-2,6,4) (Ar#); or C6H2{C(H)(2-naphthyl)2}2Me-2,6,4 (Ar¥), and one of the silyl fragments, SiMe3, SiCy3 (Cy=cyclohexyl), SiPri3, Si(p-C6H4But)3, or Si(OBor)3 (OBor=[(1S)-endo]-(−)-borneoxy). Amines including the latter silyl group represent the first enantiopure examples of this ligand class. All amines are readily deprotonated with n-butyllithium or KH. Reactions of five alkali metal amide complexes with GeCl2⋅dioxane have given monomeric amido-germanium(II) chloride complexes, LxGeCl (x=1–4, 7). Treatment of two of these with KOBut afforded monomeric amido-germanium(II) tert-butoxide species, LxGeOBut (x=1 or 3). Reductions of two amido-germanium(II) chloride systems with a dimagnesium(I) compound afforded amido-digermyne species, LxGeGeLx (x=3 or 4), the X-ray crystal structures of which show them to possess very short Ge−Ge bonds, with considerable implied multiple bond character.

Original languageEnglish
Article numbere202200303
Number of pages10
JournalZeitschrift fuer Anorganische und Allgemeine Chemie
Volume649
Issue number4
DOIs
Publication statusPublished - 13 Feb 2023

Keywords

  • amide
  • digermyne
  • germanium(I)
  • germanium(II)
  • steric bulk

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