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Synthesis, spectroscopic and structural systematics of complexes of Germanium(IV) Halides (GeX4, X = F, Cl, Br or I) with mono-, bi- and tri-Dentate and Macrocyclic Nitrogen Donor Ligands

Synthesis, spectroscopic and structural systematics of complexes of Germanium(IV) Halides (GeX4, X = F, Cl, Br or I) with mono-, bi- and tri-Dentate and Macrocyclic Nitrogen Donor Ligands
Synthesis, spectroscopic and structural systematics of complexes of Germanium(IV) Halides (GeX4, X = F, Cl, Br or I) with mono-, bi- and tri-Dentate and Macrocyclic Nitrogen Donor Ligands
The six-coordinate adducts cis-[GeX4(L-L)] (L-L = 2,2-bipyridyl, 1,10-phenanthroline, or Me2NCH2CH2NMe2, X = F, Cl or Br) have been synthesised and characterised by IR and VT 1H and 19F{1H} NMR spectroscopy. X-ray crystal structures reveal distorted octahedral geometries and the trends in d(Ge-N) with halide are interpreted in terms of varying Lewis acidity within the series. The trans-[GeX4(py)2] were similarly characterised. In contrast, GeI4 does not form similar adducts, although it appears to co-crystallise with some of the ligands, and the structure of GeI4·(1,10-phenH)3·I3 which contains phenanthrolinium cations, iodide anions and tetrahedral GeI4 molecules is reported. Multidentate nitrogen donor ligands including cyclam (1,4,8,11-tetraazacyclotetradecane) and Me4-cyclam (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) react with [GeF4(MeCN)2] to form insoluble compounds [{GeF4}2(macrocycle)] (F4N2 donor sets). In contrast, Me3[9]aneN3 (1,4,7-trimethyl-1,4,7-triazacyclononane) forms the cation [GeF3{Me3[9]aneN3}]+ with a facial geometry (N3F3 donor set) which is the first example of displacement of fluoride from GeF4 by a neutral ligand.
germanium, nitrogen ligands, fluorido complexes
1434-1948
4897-4905
Cheng, Fei
a0339c70-2a78-4078-8845-62759ac926d3
Davis, Martin F.
72f26f03-4bbe-482e-b8a5-6c792b22fcc3
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
Davis, Martin F.
72f26f03-4bbe-482e-b8a5-6c792b22fcc3
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, Davis, Martin F., Hector, Andrew L., Levason, William, Reid, Gillian, Webster, Michael and Zhang, Wenjian (2007) Synthesis, spectroscopic and structural systematics of complexes of Germanium(IV) Halides (GeX4, X = F, Cl, Br or I) with mono-, bi- and tri-Dentate and Macrocyclic Nitrogen Donor Ligands. European Journal of Inorganic Chemistry, 2007 (31), 4897-4905. (doi:10.1002/ejic.200700727).

Record type: Article

Abstract

The six-coordinate adducts cis-[GeX4(L-L)] (L-L = 2,2-bipyridyl, 1,10-phenanthroline, or Me2NCH2CH2NMe2, X = F, Cl or Br) have been synthesised and characterised by IR and VT 1H and 19F{1H} NMR spectroscopy. X-ray crystal structures reveal distorted octahedral geometries and the trends in d(Ge-N) with halide are interpreted in terms of varying Lewis acidity within the series. The trans-[GeX4(py)2] were similarly characterised. In contrast, GeI4 does not form similar adducts, although it appears to co-crystallise with some of the ligands, and the structure of GeI4·(1,10-phenH)3·I3 which contains phenanthrolinium cations, iodide anions and tetrahedral GeI4 molecules is reported. Multidentate nitrogen donor ligands including cyclam (1,4,8,11-tetraazacyclotetradecane) and Me4-cyclam (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) react with [GeF4(MeCN)2] to form insoluble compounds [{GeF4}2(macrocycle)] (F4N2 donor sets). In contrast, Me3[9]aneN3 (1,4,7-trimethyl-1,4,7-triazacyclononane) forms the cation [GeF3{Me3[9]aneN3}]+ with a facial geometry (N3F3 donor set) which is the first example of displacement of fluoride from GeF4 by a neutral ligand.

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More information

Published date: 10 September 2007
Keywords: germanium, nitrogen ligands, fluorido complexes

Identifiers

Local EPrints ID: 148209
URI: https://eprints.soton.ac.uk/id/eprint/148209
ISSN: 1434-1948
PURE UUID: b1a584bb-b833-47d3-8eca-0d52a0c5f9b4
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: 03 Jun 2010 13:16
Last modified: 15 Aug 2019 00:57

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