Synthesis and structural characterisation of germanium(II) halide complexes with neutral N-donor ligands

Francesco Ferrante, Wenjian Zhang, John M. Dyke, Fei Cheng, Andrew L. Hector, William Levason, Michael Webster, Gillian Reid

Risultato della ricerca: Article

37 Citazioni (Scopus)

Abstract

The Ge(II) complexes [GeX2(L–L)] (L–L = 1,10-phen (X = Cl, Br); L–L = Me2N(CH2)2NMe2,2,2¢-bipy (X = Cl)), [GeX(L–L)][GeX3] (L–L = 2,2¢-bipy (X = Br); L–L = pmdta(MeN(CH2CH2NMe2)2) (X = Cl, Br)) have been prepared and their crystal structures determined. Thecrystal structure of [GeCl2{Me2N(CH2)2NMe2}] shows a weakly associated centrosymmetric dimerbased upon distorted square-pyramidal coordination at Ge(II) and containing asymmetrically chelatingdiamine ligands. The structure of [GeCl2(2,2¢-bipy)] contains a chelating 2,2¢-bipy ligand and forms azig-zag chain polymer via long-range intermolecular Ge ◊◊◊ Cl bridging interactions, leading to a verydistorted six-coordinate environment at Ge. [GeCl2(1,10-phen)] adopts a weakly associated dimericstructure similar to that in [GeCl2{Me2N(CH2)2NMe2}], whereas [GeBr2(1,10-phen)] is again a zig-zagpolymer similar to [GeCl2(2,2¢-bipy)]. [GeBr(2,2¢-bipy)][GeBr3] contains a pyramidal cation with achelating 2,2¢-bipy and a terminal Br ligand and with long-range contacts involving the three Br atomsin the anion. [GeX(pmdta)][GeX3] (X = Cl or Br) show discrete cations and anions, with no significantlong-range interactions. The bonding in these systems can be described as covalent, with longer rangeinteractions to other ligands involving the 4p orbitals of Ge. DFT calculations performed on[GeCl2(2,2¢-bipy)] show that the geometry of the monomer unit in the experimental crystal structuredoes not correspond to the global minimum of the isolated molecule, but to a higher energy minimum.In contrast, the calculated structure of the tetramer shows some of the main structural characteristicsobserved in the crystal structure.
Lingua originaleEnglish
pagine (da-a)847-856
Numero di pagine10
RivistaDalton Transactions
Volume39
Stato di pubblicazionePublished - 2010

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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    Ferrante, F., Zhang, W., Dyke, J. M., Cheng, F., Hector, A. L., Levason, W., Webster, M., & Reid, G. (2010). Synthesis and structural characterisation of germanium(II) halide complexes with neutral N-donor ligands. Dalton Transactions, 39, 847-856.