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Silylated Ge9 Clusters as New Ligands for Cyclic (Alkyl)amino and Mesoionic Carbene Copper Complexes.
Schiegerl, Lorenz J; Melaimi, Mohand; Tolentino, Daniel R; Klein, Wilhelm; Bertrand, Guy; Fässler, Thomas F.
Afiliação
  • Schiegerl LJ; Department of Chemistry , Technische Universität München (TUM) , Lichtenbergstraße 4 , 85748 Garching , Germany.
  • Melaimi M; UCSD-CNRS Joint Research Chemistry Laboratory (UMI 3555) , University of California-San Diego , La Jolla , California 92093-0353 , United States.
  • Tolentino DR; UCSD-CNRS Joint Research Chemistry Laboratory (UMI 3555) , University of California-San Diego , La Jolla , California 92093-0353 , United States.
  • Klein W; Department of Chemistry , Technische Universität München (TUM) , Lichtenbergstraße 4 , 85748 Garching , Germany.
  • Bertrand G; UCSD-CNRS Joint Research Chemistry Laboratory (UMI 3555) , University of California-San Diego , La Jolla , California 92093-0353 , United States.
  • Fässler TF; Department of Chemistry , Technische Universität München (TUM) , Lichtenbergstraße 4 , 85748 Garching , Germany.
Inorg Chem ; 58(5): 3256-3264, 2019 Mar 04.
Article em En | MEDLINE | ID: mdl-30741546
ABSTRACT
The coordination of Ge9 Zintl clusters at (carbene)CuI moieties is explored, and the complexes [(CAAC)Cu]2[η3-Ge9{Si(TMS)3}2] (1), (CAAC)Cu[η3-Ge9{Si(TMS)3}3] (2), and (MIC)Cu[η3-Ge9{Si(TMS)3}3] (3) are compared with their known N-heterocyclic carbene (NHC) derivatives (A and B), where CAAC = cyclic (alkyl)amino carbene, MIC = mesoionic carbene, and TMS = trimethylsilane. In analogy to the NHC derivatives, the synthesis of 1-3 proceeds by single-step reactions of (CAAC)CuCl or (MIC)CuCl with the [Ge9R2]2- and [Ge9R3]- [R = Si(TMS)3] cluster ligands, respectively, and yields complexes of (carbene)CuI (carbene = CAAC, MIC) moieties exhibiting η3-coordination modes of the Ge9 deltahedron to the Cu atom. In 1, [Ge9R2]2- acts as a η3-bridging unit for two (CAAC)CuI moieties, and 2 and 3 feature single (carbene)CuI (CAAC and MIC) fragments η3-connected to [Ge9R3]- units. Analysis of the bond lengths in comparison with known examples shows a bond expansion within the coordinated Ge3 triangular faces for all (carbene)CuIGe9 complexes (carbene = NHC, MIC, CAAC). All compounds are characterized by single-crystal X-ray diffractometry, NMR spectroscopy [1H, 13C{1H}, and 29Si{1H}], electrospray ionization mass spectometry, elemental analysis (C, H, and N), and for the first time also by IR and Raman investigations (for 2 and 3). The new complexes add to the known NHC derivatives and extend the exploration of Ge9 clusters with carbene ligands at CuI atoms.

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Inorg Chem Ano de publicação: 2019 Tipo de documento: Article País de afiliação: Alemanha

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Inorg Chem Ano de publicação: 2019 Tipo de documento: Article País de afiliação: Alemanha
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