Synthesis and Reactivity Studies of Amido-Substituted Germanium(I)/Tin(I) Dimers and Clusters

John A. Kelly, Martin Juckel, Terrance J. Hadlington, Israel Fernández, Gernot Frenking, Cameron Jones

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Three amide ligands of varying steric bulk and electronic properties were utilized to prepare a series of amido-germanium(II)/tin(II) halide compounds, (LEX) n , (L= -N{B(DipNCH) 2 }(SiMe 3 ), TBo L; -N{B(DipNCH) 2 }(SiPh 3 ), PhBo L; -N(Dip)(tBu), DBu L; Dip=C 6 H 3 iPr 2 -2,6; E=Ge or Sn; X=Cl or Br; n=1 or 2). Reductions of these with a magnesium(I) dimer, {( Mes Nacnac)Mg} 2 ( Mes Nacnac=[(MesNCMe) 2 CH] , Mes=mesityl), afforded singly bonded amido-digermynes ( TBo LGe−Ge TBo L and PhBo LGe−Ge PhBo L), and an amido-distannyne ( PhBo LSn−Sn PhBo L), in addition to several low-valent, amido stabilized tetrel–tetrel bonded cluster compounds, ( DBu LGe) 4 , ( DBu LSn) 6 and Sn 5 ( TBo L) 4 . The nature of the products resulting from these reactions was largely dependent on the steric bulk of the amide ligand employed. Cluster ( DBu LGe) 4 possessed an unusual folded butterfly structure, the bonding and electronic of which were examined using DFT calculations. Reactions of the amido-germanium(I) compounds with H 2 were explored, and gave rise to the amido-digermene, TBo L(H)Ge=Ge(H) TBo L and the cyclotetragermane, { DBu L(H)Ge} 4 . Reactions of ( DBu LGe) 4 with a series of unsaturated small molecule substrates yielded DBu LGeOGe DBu L, DBu LGe(μ-C 2 H 4 ) 2 Ge DBu L and DBu LGe(μ-1,4-C 6 H 8 )(μ-1,2-C 6 H 8 )Ge DBu L. The latter results imply that ( DBu LGe) 4 can act as a masked source of the digermyne DBu LGeGe DBu L in these reactions. All further reactivity studies indicated that the germanium(I) compounds exhibit a “transition-metal-like” behavior, which is closely related to that previously described for bulky digermynes and related compounds.

Original languageEnglish
Pages (from-to)2773-2785
Number of pages13
JournalChemistry - A European Journal
Issue number11
Publication statusPublished - 21 Feb 2019


  • cluster compounds
  • digermyne
  • distannyne
  • germanium
  • tin

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