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Diphosphine and diarsine complexes of germanium(II) halides—preparation, spectroscopic and structural studies

Diphosphine and diarsine complexes of germanium(II) halides—preparation, spectroscopic and structural studies
Diphosphine and diarsine complexes of germanium(II) halides—preparation, spectroscopic and structural studies
The Ge(II) halide complexes [GeX2(L?L)] (L?L = o-C6H4(PPh2)2, o-C6H4(PMe2)2, Me2P(CH2)2PMe2; X = Cl, Br, I. L?L = Et2P(CH2)2PEt2; X = Cl or Br. L?L = o-C6H4(AsMe2)2; X = Br or I) and [GeCl(L?L)][GeCl3] (L?L = o-C6H4(AsMe2)2) have been prepared and characterized by IR, 1H and 31P{1H} NMR spectroscopy, and microanalyses. The crystal structures of [GeX2{o-C6H4(PPh2)2}] (X = Cl, Br, I) reveal discrete mononuclear units with a very asymmetric bidentate o-C6H4(PPh2)2 ligand and a bent GeX2 unit.

Those of [GeX2{o-C6H4(PMe2)2}] show symmetrically coordinated diphosphine with loosely associated dimer arrangements, formed through long Ge···X bridges between adjacent monomer units. [GeX2{R2P(CH2)2PR2}] (R = Me; X = Cl, Br, I. R = Et; X = Cl, Br) all show discrete monomer structures with 2-fold crystallographic symmetry and based upon four-coordinate Ge, with the diphosphine chelating and approximately linear GeX2 units. [GeI2{o-C6H4(AsMe2)2}] involves significant intermolecular Ge···I interactions, giving rise to a zigzag polymer chain.

Finally, the structure of [GeCl{o-C6H4(AsMe2)2}][GeCl3] shows pyramidal cations and anions both with crystallographic mirror symmetry, with the diarsine symmetrically chelating, and long Ge···Cl interactions give a loosely associated chain polymer with alternating cations and anions. Comparisons across this series of structurally diverse complexes are discussed.

0020-1669
752-760
Cheng, Fei
a0339c70-2a78-4078-8845-62759ac926d3
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
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, Hector, Andrew L., Levason, William, Reid, Gillian, Webster, Michael and Zhang, Wenjian (2009) Diphosphine and diarsine complexes of germanium(II) halides—preparation, spectroscopic and structural studies. Inorganic Chemistry, 49 (2), 752-760. (doi:10.1021/ic902068z).

Record type: Article

Abstract

The Ge(II) halide complexes [GeX2(L?L)] (L?L = o-C6H4(PPh2)2, o-C6H4(PMe2)2, Me2P(CH2)2PMe2; X = Cl, Br, I. L?L = Et2P(CH2)2PEt2; X = Cl or Br. L?L = o-C6H4(AsMe2)2; X = Br or I) and [GeCl(L?L)][GeCl3] (L?L = o-C6H4(AsMe2)2) have been prepared and characterized by IR, 1H and 31P{1H} NMR spectroscopy, and microanalyses. The crystal structures of [GeX2{o-C6H4(PPh2)2}] (X = Cl, Br, I) reveal discrete mononuclear units with a very asymmetric bidentate o-C6H4(PPh2)2 ligand and a bent GeX2 unit.

Those of [GeX2{o-C6H4(PMe2)2}] show symmetrically coordinated diphosphine with loosely associated dimer arrangements, formed through long Ge···X bridges between adjacent monomer units. [GeX2{R2P(CH2)2PR2}] (R = Me; X = Cl, Br, I. R = Et; X = Cl, Br) all show discrete monomer structures with 2-fold crystallographic symmetry and based upon four-coordinate Ge, with the diphosphine chelating and approximately linear GeX2 units. [GeI2{o-C6H4(AsMe2)2}] involves significant intermolecular Ge···I interactions, giving rise to a zigzag polymer chain.

Finally, the structure of [GeCl{o-C6H4(AsMe2)2}][GeCl3] shows pyramidal cations and anions both with crystallographic mirror symmetry, with the diarsine symmetrically chelating, and long Ge···Cl interactions give a loosely associated chain polymer with alternating cations and anions. Comparisons across this series of structurally diverse complexes are discussed.

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Published date: 17 December 2009

Identifiers

Local EPrints ID: 145933
URI: https://eprints.soton.ac.uk/id/eprint/145933
ISSN: 0020-1669
PURE UUID: d0646734-2618-4a49-9dd9-9fb87466c7db
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 09:18
Last modified: 14 Jul 2018 00:37

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