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

Synthesis and structural characterisation of germanium(II) halide complexes with neutral N-donor ligands
Synthesis and structural characterisation of germanium(II) halide complexes with neutral N-donor ligands
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 GeCl 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.
0300-9246
847-856
Cheng, Fei
a0339c70-2a78-4078-8845-62759ac926d3
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Ferrante, Francesco
5b217df6-ac83-4b5d-85c3-96060e69b89a
Hector, Andrew L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Cheng, Fei
a0339c70-2a78-4078-8845-62759ac926d3
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Ferrante, Francesco
5b217df6-ac83-4b5d-85c3-96060e69b89a
Hector, Andrew L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Cheng, Fei, Dyke, John M., Ferrante, Francesco, Hector, Andrew L., Levason, William, Reid, Gillian, Webster, Michael and Zhang, Wenjian (2010) Synthesis and structural characterisation of germanium(II) halide complexes with neutral N-donor ligands. Dalton Transactions, 39 (3), 847-856. (doi:10.1039/b911016j).

Record type: Article

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 GeCl 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.

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Published date: 2010
Organisations: Chemistry

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Local EPrints ID: 145937
URI: https://eprints.soton.ac.uk/id/eprint/145937
ISSN: 0300-9246
PURE UUID: a8ad09fb-9a35-424c-a4d7-3001357b6e03
ORCID for John M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X
ORCID for Andrew L. Hector: ORCID iD orcid.org/0000-0002-9964-2163
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 20 Apr 2010 09:14
Last modified: 14 Jul 2018 00:37

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Author: Fei Cheng
Author: John M. Dyke ORCID iD
Author: Francesco Ferrante
Author: William Levason ORCID iD
Author: Gillian Reid ORCID iD
Author: Michael Webster
Author: Wenjian Zhang

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