TY - JOUR
T1 - Development of a Library of Extremely Bulky Amide Ligands, and their use for the Stabilization of Germanium(I) and Germanium(II) Compounds
AU - Garg, Palak
AU - Dange, Deepak
AU - Jones, Cameron
N1 - Funding Information:
CJ thanks the ustralian Research Council and the US Air Force Asian Office of Aerospace Research and Development (grant FA2386‐21‐1‐4048). Part of this research was undertaken on the MX1 beam line at the Australian Synchrotron, Victoria, Australia. Open Access publishing facilitated by Monash University, as part of the Wiley ‐ Monash University agreement via the Council of Australian University Librarians.
Publisher Copyright:
© 2022 The Authors. Zeitschrift für anorganische und allgemeine Chemie published by Wiley-VCH GmbH.
PY - 2023/2/13
Y1 - 2023/2/13
N2 - 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.
AB - 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.
KW - amide
KW - digermyne
KW - germanium(I)
KW - germanium(II)
KW - steric bulk
UR - http://www.scopus.com/inward/record.url?scp=85139974568&partnerID=8YFLogxK
U2 - 10.1002/zaac.202200303
DO - 10.1002/zaac.202200303
M3 - Article
AN - SCOPUS:85139974568
SN - 0044-2313
VL - 649
JO - Zeitschrift fuer Anorganische und Allgemeine Chemie
JF - Zeitschrift fuer Anorganische und Allgemeine Chemie
IS - 4
M1 - e202200303
ER -