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Selenoether macrocyclic chemistry—syntheses and properties of new potentially tridentate and hexadentate Se/O-donor macrocycles

Selenoether macrocyclic chemistry—syntheses and properties of new potentially tridentate and hexadentate Se/O-donor macrocycles
Selenoether macrocyclic chemistry—syntheses and properties of new potentially tridentate and hexadentate Se/O-donor macrocycles
Treatment of O(CH2CH2SeCN)2 with Na in NH3(l), followed by dropwise addition of a thf solution of o-C6H4(CH2Br)2 at -40 °C leads to formation of three mixed Se/O-donor macrocycles which are separable by column chromatography, the [1 + 1] species L1, the [2 + 2] ring L2 and the [3 + 3] ring L3, of which L2 is by far the major species. Using the same starting materials, but in a high dilution cyclisation at room temperature with NaBH4 in thf/EtOH gives exclusively the [1 + 1] ring, L1. The saturated ring Se/O-donor macrocycles, L4 and L5 are obtained by simultaneous dropwise addition of solutions of O(CH2CH2SeCN)2 and Br(CH2)3Br to NaBH4 suspended in thf/EtOH. The small tridentate Se2O-donor ring, L4, is again the dominant product under these conditions (71%), although the more flexible precursors in this reaction also give rise to the larger Se4O2-donor ring, L5, as a by-product in 8% yield. These compounds are readily separated and purified by column chromatography (ethyl acetate:hexane, 1:19). The new macrocycles have been characterised by 1H, 13C{1H} and 77Se{1H} NMR spectroscopy and mass spectrometry, together with crystal structures of L1 and L2. Complexes of L1 and L2 with late transition metals (Pd(II), Pt(II), Cu(I) and Ag(I)) are also described.
coordinating properties, anese(4)=1, selenium coronands, 9, 13-tetraselenacyclohexadecane, thio-ether, ligands, crown-ethers, 5, crystal-structures, complexes, br, x-ray structure
1477-9226
3486-3492
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Manning, Joanna M.
071c4af0-0d09-422a-8ca3-d5a9454d587a
Nirwan, Manisha
5326a14f-3c10-407b-bebe-272f53d6b9cb
Ratnani, Raju
0a86c56f-00c6-4c9f-8aa0-52667938ba70
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Smith, Hayley L.
2159f777-2a20-46d5-be86-3d0771fdaa71
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Manning, Joanna M.
071c4af0-0d09-422a-8ca3-d5a9454d587a
Nirwan, Manisha
5326a14f-3c10-407b-bebe-272f53d6b9cb
Ratnani, Raju
0a86c56f-00c6-4c9f-8aa0-52667938ba70
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Smith, Hayley L.
2159f777-2a20-46d5-be86-3d0771fdaa71
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

Levason, William, Manning, Joanna M., Nirwan, Manisha, Ratnani, Raju, Reid, Gillian, Smith, Hayley L. and Webster, Michael (2008) Selenoether macrocyclic chemistry—syntheses and properties of new potentially tridentate and hexadentate Se/O-donor macrocycles. Dalton Transactions, (26), 3486-3492. (doi:10.1039/b718950h).

Record type: Article

Abstract

Treatment of O(CH2CH2SeCN)2 with Na in NH3(l), followed by dropwise addition of a thf solution of o-C6H4(CH2Br)2 at -40 °C leads to formation of three mixed Se/O-donor macrocycles which are separable by column chromatography, the [1 + 1] species L1, the [2 + 2] ring L2 and the [3 + 3] ring L3, of which L2 is by far the major species. Using the same starting materials, but in a high dilution cyclisation at room temperature with NaBH4 in thf/EtOH gives exclusively the [1 + 1] ring, L1. The saturated ring Se/O-donor macrocycles, L4 and L5 are obtained by simultaneous dropwise addition of solutions of O(CH2CH2SeCN)2 and Br(CH2)3Br to NaBH4 suspended in thf/EtOH. The small tridentate Se2O-donor ring, L4, is again the dominant product under these conditions (71%), although the more flexible precursors in this reaction also give rise to the larger Se4O2-donor ring, L5, as a by-product in 8% yield. These compounds are readily separated and purified by column chromatography (ethyl acetate:hexane, 1:19). The new macrocycles have been characterised by 1H, 13C{1H} and 77Se{1H} NMR spectroscopy and mass spectrometry, together with crystal structures of L1 and L2. Complexes of L1 and L2 with late transition metals (Pd(II), Pt(II), Cu(I) and Ag(I)) are also described.

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More information

Published date: 2008
Keywords: coordinating properties, anese(4)=1, selenium coronands, 9, 13-tetraselenacyclohexadecane, thio-ether, ligands, crown-ethers, 5, crystal-structures, complexes, br, x-ray structure
Organisations: Chemistry

Identifiers

Local EPrints ID: 146975
URI: http://eprints.soton.ac.uk/id/eprint/146975
ISSN: 1477-9226
PURE UUID: b70ec41f-5c1c-4af0-af4e-47c39051618a
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

Catalogue record

Date deposited: 23 Apr 2010 08:29
Last modified: 19 Nov 2019 02:04

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