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The structural and stereogenic properties of pentaerythritoxy-bridged cyclotriphosphazene derivatives: spiro-spiro, spiro-ansa and ansa-ansa isomers

The structural and stereogenic properties of pentaerythritoxy-bridged cyclotriphosphazene derivatives: spiro-spiro, spiro-ansa and ansa-ansa isomers
The structural and stereogenic properties of pentaerythritoxy-bridged cyclotriphosphazene derivatives: spiro-spiro, spiro-ansa and ansa-ansa isomers
Reactions of pentaerythritol with hexachlorocyclotriphosphazene, N3P3Cl6, and gem-disubstituted cyclotriphosphazene derivatives, N3P3Cl4R2 [R = Ph, NHBut or (OCH2CF2CF2CH2O)(0.5)] gave a series of pentaerythritol-bridged derivatives linked spiro-spiro, spiro-ansa and ansa-ansa. The structures and stereogenic properties of the products were characterised by X-ray crystallography and P-31 NMR spectroscopy on addition of the chiral solvating agent, (S)-(+)-2,2,2-trifluoro-1-(9-anthryl)ethanol. Molecules with spiro-spiro and spiro-ansa bridged gem-disubstituted cyclophosphazenes [R = Ph, NHBut or (OCH2CF2CF2CH2O) 0.5] are found to be chiral and exist as racemates. Molecules with ansa-ansa bridged cyclophosphazenes [R = Cl or (OCH2CF2CF2CH2O) 0.5] have been characterised for the first time and are shown to have meso configurations. Analysis of crystal structure data shows that the six-membered chair form of the spiro rings and the eight-membered boat-chair form of the ansa rings in the bridged compounds are similar to analogous spiro and ansa exocyclic ring conformations of 1,3-propanedioxy-derivatives of cyclophosphazenes.
phosphorus-nitrogen-compounds, ray crystal-structures, substituent constants, n3p3cl22 derivatives, phosphazene chemistry, nmr-spectra, 1st example, basicity, hexachlorocyclotriphosphazatriene, cyclophosphazenes
1477-9226
1302-1312
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Eaton, Robert J.
e274676b-0499-47e1-8dbb-8d1ed908cdea
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kiliç, Adem
53892b58-c3f9-4894-bdf9-6be70ab7611e
Shaw, Robert A.
a9ecde60-6fe9-4b5d-86e3-77cd5dcfaab8
Uslu, Aylin
95af2437-3473-4022-8070-ad7d36524a87
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Eaton, Robert J.
e274676b-0499-47e1-8dbb-8d1ed908cdea
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kiliç, Adem
53892b58-c3f9-4894-bdf9-6be70ab7611e
Shaw, Robert A.
a9ecde60-6fe9-4b5d-86e3-77cd5dcfaab8
Uslu, Aylin
95af2437-3473-4022-8070-ad7d36524a87

Coles, Simon J., Davies, David B., Eaton, Robert J., Hursthouse, Michael B., Kiliç, Adem, Shaw, Robert A. and Uslu, Aylin (2006) The structural and stereogenic properties of pentaerythritoxy-bridged cyclotriphosphazene derivatives: spiro-spiro, spiro-ansa and ansa-ansa isomers. Dalton Transactions, (10), 1302-1312. (doi:10.1039/b512854d).

Record type: Article

Abstract

Reactions of pentaerythritol with hexachlorocyclotriphosphazene, N3P3Cl6, and gem-disubstituted cyclotriphosphazene derivatives, N3P3Cl4R2 [R = Ph, NHBut or (OCH2CF2CF2CH2O)(0.5)] gave a series of pentaerythritol-bridged derivatives linked spiro-spiro, spiro-ansa and ansa-ansa. The structures and stereogenic properties of the products were characterised by X-ray crystallography and P-31 NMR spectroscopy on addition of the chiral solvating agent, (S)-(+)-2,2,2-trifluoro-1-(9-anthryl)ethanol. Molecules with spiro-spiro and spiro-ansa bridged gem-disubstituted cyclophosphazenes [R = Ph, NHBut or (OCH2CF2CF2CH2O) 0.5] are found to be chiral and exist as racemates. Molecules with ansa-ansa bridged cyclophosphazenes [R = Cl or (OCH2CF2CF2CH2O) 0.5] have been characterised for the first time and are shown to have meso configurations. Analysis of crystal structure data shows that the six-membered chair form of the spiro rings and the eight-membered boat-chair form of the ansa rings in the bridged compounds are similar to analogous spiro and ansa exocyclic ring conformations of 1,3-propanedioxy-derivatives of cyclophosphazenes.

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More information

Published date: 2006
Keywords: phosphorus-nitrogen-compounds, ray crystal-structures, substituent constants, n3p3cl22 derivatives, phosphazene chemistry, nmr-spectra, 1st example, basicity, hexachlorocyclotriphosphazatriene, cyclophosphazenes

Identifiers

Local EPrints ID: 44410
URI: https://eprints.soton.ac.uk/id/eprint/44410
ISSN: 1477-9226
PURE UUID: bf035951-511f-42f3-b951-fef4f20409cd
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 01 Mar 2007
Last modified: 14 Mar 2019 01:48

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