Development of a Library of Extremely Bulky Amide Ligands, and their use for the Stabilization of Germanium(I) and Germanium(II) Compounds. Issue 4 (17th October 2022)

• Record Type: Journal Article
• Authors: Garg, Palak; Dange, Deepak; Jones, Cameron
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 649:Issue 4(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-10-17
• Subjects: amide -- steric bulk -- germanium(II) -- germanium(I) -- digermyne; Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.202200303
• Languages: English
• ISSNs: 0044-2313

Abstract

Abstract: Eleven new extremely bulky aryl/silyl substituted secondary amines, L 1–11 H, have been prepared. These incorporate a combination of one of the bulky aryl groups, C6 H2 {C(H)Ph2 }2 R‐2, 6, 4; R=Me (Ar*), Pr i (Ar † ); C6 H2 {C(H)(C6 H3 Bu t 2 ‐3, 5)2 }2 Me‐2, 6, 4) (Ar # ); or C6 H2 {C(H)(2‐naphthyl)2 }2 Me‐2, 6, 4 (Ar ¥ ), and one of the silyl fragments, SiMe3, SiCy3 (Cy=cyclohexyl), SiPr i 3, Si( p ‐C6 H4 Bu t )3, or Si(OBor)3 (OBor=[(1 S )‐ 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, L x GeCl (x=1–4, 7). Treatment of two of these with KOBu t afforded monomeric amido‐germanium(II) tert ‐butoxide species, L x GeOBu t (x=1 or 3). Reductions of two amido‐germanium(II) chloride systems with a dimagnesium(I) compound afforded amido‐digermyne species, L x GeGeL x (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. Abstract :