Synthesis, Characterization, and Reaction of Digermylenes

Abstract

A series of digermylenes R(EGeL) 2 (L = CH[C(Me)N-(Ar)] 2 , Ar = 2,6-iPr 2 C 6 H 3 ; E = O, R = 1,3-C 6 H 4 (1), 1,4-C 6 H 4 (2), Me 2 C(CH 2 ) 2 (3); E = NH, R = 1,4-C 6 H 4 (4), 1,4-C 6 H 10 (5); E = C(O)O, R = 1,3-C 6 H 4 (6)) were synthesized by the reactions of L'Ge (L' = HC[C(CH 2 )N(Ar)]C(Me)N(Ar), Ar = 2,6-iPr 2 C 6 H 3 ) with selected diphenols, diol, diamines, and o-/m-phthalic acids, respectively. Treatment of digermylene 1,3-C 6 H 4 (OGeL) 2 (1) with sulfur, selenium and CuX (X = Cl, Br, I) led to the formation of 1,3-C 6 H 4 [OGe(S)L] 2 (8), 1,3-C 6 H 4 [OGe(Se)L] 2 (9), and (CuX) 2 [1,3-C 6 H 4 (OGeL) 2 ] 2 (X = Cl (10), Br (11), I ( 12)), respectively. The obtained products were characterized by melting point, elemental analysis, FT-IR, 1 H and 13 C NMR spectroscopy, and single-crystal X-ray diffraction.

σ,π‐Conjugated Bis(germylene) Adducts with NHC and CAACs

“…Neither NHC nor CAAC adducts of bridged bis(tetrylenes) with organic or inorganic linking units have been reported, presumably because known bis(tetrylenes) are without exception stabilized by internal donation of adjacent n‐donor substituents at both tetrel(II) centers [32–57] . The thus reduced electron deficiency is obviously detrimental to formation of adducts with external donors.…”