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Synthesis and Reactivity Studies of Amido‐Substituted Germanium(I)/Tin(I) Dimers and Clusters
Author(s) -
Kelly John A.,
Juckel Martin,
Hadlington Terrance J.,
Fernández Israel,
Frenking Gernot,
Jones Cameron
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201804770
Subject(s) - chemistry , steric effects , tin , germanium , amide , reactivity (psychology) , halide , crystallography , ligand (biochemistry) , dimer , molecule , cluster (spacecraft) , stereochemistry , medicinal chemistry , inorganic chemistry , organic chemistry , silicon , medicine , biochemistry , alternative medicine , receptor , pathology , computer science , programming language
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)( t Bu), DBu L; Dip=C 6 H 3 i Pr 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.