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

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

Risultato della ricerca: Article

34 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. The crystal structure of [GeCl2{Me2N(CH2)2NMe2}] shows a weakly associated centrosymmetric dimer based upon distorted square-pyramidal coordination at Ge(II) and containing asymmetrically chelating diamine ligands. The structure of [GeCl2(2,2¢-bipy)] contains a chelating 2,2¢-bipy ligand and forms a zig-zag chain polymer via long-range intermolecular Ge ◊◊◊ Cl bridging interactions, leading to a very distorted six-coordinate environment at Ge. [GeCl2(1,10-phen)] adopts a weakly associated dimeric structure similar to that in [GeCl2{Me2N(CH2)2NMe2}], whereas [GeBr2(1,10-phen)] is again a zig-zag polymer similar to [GeCl2(2,2¢-bipy)]. [GeBr(2,2¢-bipy)][GeBr3] contains a pyramidal cation with a chelating 2,2¢-bipy and a terminal Br ligand and with long-range contacts involving the three Br atoms in the anion. [GeX(pmdta)][GeX3] (X = Cl or Br) show discrete cations and anions, with no significant long-range interactions. The bonding in these systems can be described as covalent, with longer range interactions 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 structure does 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 characteristics observed in the crystal structure.
Lingua originaleEnglish
pagine (da-a)847-856
Numero di pagine10
RivistaDalton Transactions
Volume39
Stato di pubblicazionePublished - 2010

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Germanium
Ligands
Anions
Cations
Crystal structure
Chelation
Discrete Fourier transforms
Polymers
Monomers
Crystals
Molecules
Geometry

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cita questo

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

Synthesis and structural characterisation of germanium(II) halide complexes with neutral N-donor ligands. / Ferrante, Francesco; Hector, Andrew L.; Levason, William; Webster, Michael; Reid, Gillian; Zhang, Wenjian; Dyke, John M.; Cheng, Fei.

In: Dalton Transactions, Vol. 39, 2010, pag. 847-856.

Risultato della ricerca: Article

Ferrante, F, Hector, AL, Levason, W, Webster, M, Reid, G, Zhang, W, Dyke, JM & Cheng, F 2010, 'Synthesis and structural characterisation of germanium(II) halide complexes with neutral N-donor ligands', Dalton Transactions, vol. 39, pagg. 847-856.
Ferrante, Francesco ; Hector, Andrew L. ; Levason, William ; Webster, Michael ; Reid, Gillian ; Zhang, Wenjian ; Dyke, John M. ; Cheng, Fei. / Synthesis and structural characterisation of germanium(II) halide complexes with neutral N-donor ligands. In: Dalton Transactions. 2010 ; Vol. 39. pagg. 847-856.
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title = "Synthesis and structural characterisation of germanium(II) halide complexes with neutral N-donor ligands",
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. The crystal structure of [GeCl2{Me2N(CH2)2NMe2}] shows a weakly associated centrosymmetric dimer based upon distorted square-pyramidal coordination at Ge(II) and containing asymmetrically chelating diamine ligands. The structure of [GeCl2(2,2¢-bipy)] contains a chelating 2,2¢-bipy ligand and forms a zig-zag chain polymer via long-range intermolecular Ge ◊◊◊ Cl bridging interactions, leading to a very distorted six-coordinate environment at Ge. [GeCl2(1,10-phen)] adopts a weakly associated dimeric structure similar to that in [GeCl2{Me2N(CH2)2NMe2}], whereas [GeBr2(1,10-phen)] is again a zig-zag polymer similar to [GeCl2(2,2¢-bipy)]. [GeBr(2,2¢-bipy)][GeBr3] contains a pyramidal cation with a chelating 2,2¢-bipy and a terminal Br ligand and with long-range contacts involving the three Br atoms in the anion. [GeX(pmdta)][GeX3] (X = Cl or Br) show discrete cations and anions, with no significant long-range interactions. The bonding in these systems can be described as covalent, with longer range interactions 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 structure does 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 characteristics observed in the crystal structure.",
keywords = "germanium(II) complexes, structure identification",
author = "Francesco Ferrante and Hector, {Andrew L.} and William Levason and Michael Webster and Gillian Reid and Wenjian Zhang and Dyke, {John M.} and Fei Cheng",
year = "2010",
language = "English",
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journal = "Dalton Transactions",
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TY - JOUR

T1 - Synthesis and structural characterisation of germanium(II) halide complexes with neutral N-donor ligands

AU - Ferrante, Francesco

AU - Hector, Andrew L.

AU - Levason, William

AU - Webster, Michael

AU - Reid, Gillian

AU - Zhang, Wenjian

AU - Dyke, John M.

AU - Cheng, Fei

PY - 2010

Y1 - 2010

N2 - 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. The crystal structure of [GeCl2{Me2N(CH2)2NMe2}] shows a weakly associated centrosymmetric dimer based upon distorted square-pyramidal coordination at Ge(II) and containing asymmetrically chelating diamine ligands. The structure of [GeCl2(2,2¢-bipy)] contains a chelating 2,2¢-bipy ligand and forms a zig-zag chain polymer via long-range intermolecular Ge ◊◊◊ Cl bridging interactions, leading to a very distorted six-coordinate environment at Ge. [GeCl2(1,10-phen)] adopts a weakly associated dimeric structure similar to that in [GeCl2{Me2N(CH2)2NMe2}], whereas [GeBr2(1,10-phen)] is again a zig-zag polymer similar to [GeCl2(2,2¢-bipy)]. [GeBr(2,2¢-bipy)][GeBr3] contains a pyramidal cation with a chelating 2,2¢-bipy and a terminal Br ligand and with long-range contacts involving the three Br atoms in the anion. [GeX(pmdta)][GeX3] (X = Cl or Br) show discrete cations and anions, with no significant long-range interactions. The bonding in these systems can be described as covalent, with longer range interactions 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 structure does 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 characteristics observed in the crystal structure.

AB - 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. The crystal structure of [GeCl2{Me2N(CH2)2NMe2}] shows a weakly associated centrosymmetric dimer based upon distorted square-pyramidal coordination at Ge(II) and containing asymmetrically chelating diamine ligands. The structure of [GeCl2(2,2¢-bipy)] contains a chelating 2,2¢-bipy ligand and forms a zig-zag chain polymer via long-range intermolecular Ge ◊◊◊ Cl bridging interactions, leading to a very distorted six-coordinate environment at Ge. [GeCl2(1,10-phen)] adopts a weakly associated dimeric structure similar to that in [GeCl2{Me2N(CH2)2NMe2}], whereas [GeBr2(1,10-phen)] is again a zig-zag polymer similar to [GeCl2(2,2¢-bipy)]. [GeBr(2,2¢-bipy)][GeBr3] contains a pyramidal cation with a chelating 2,2¢-bipy and a terminal Br ligand and with long-range contacts involving the three Br atoms in the anion. [GeX(pmdta)][GeX3] (X = Cl or Br) show discrete cations and anions, with no significant long-range interactions. The bonding in these systems can be described as covalent, with longer range interactions 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 structure does 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 characteristics observed in the crystal structure.

KW - germanium(II) complexes, structure identification

UR - http://hdl.handle.net/10447/44044

M3 - Article

VL - 39

SP - 847

EP - 856

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

ER -