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Structural investigations of phosphorus-nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6 - n)(NHBut)n derivatives

Structural investigations of phosphorus-nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6 - n)(NHBut)n derivatives
Structural investigations of phosphorus-nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6 - n)(NHBut)n derivatives
A series of compounds of the N3P3Cl(6 - n)(NHBut)n family (where n = 0, 1, 2, 4 and 6) are presented, and their molecular parameters are related to trends in physical properties, which provides insight into a potential reaction mechanism for nucleophilic substitution. The crystal structures of N3P3Cl5(NHBut) and N3P3Cl2(NHBut)4 have been determined at 120 K, and those of N3P3Cl6 and N3P3Cl4(NHBut)2 have been redetermined at 120 K. These are compared with the known structure of N3P3(NHBut)6 studied at 150 K. Trends in molecular parameters [phosphazene ring, P-Cl and P-N(HBut) distances, PCl2 angles, and endo- and exocyclic phosphazene ring parameters] across the series are observed. Hydrogen-bonding motifs are identified, characterized and compared. Both the molecular and the hydrogen-bonding parameters are related to the electron distribution in bonds and the derived basicities of the cyclophosphazene series of compounds. These findings provide evidence for a proposed mechanism for nucleophilic substitution at a phosphorus site bearing a PCl(NHBut) group
x-ray crystallography, crystal-structure, cl33p3n3 compounds, molecular-parameters, basicity constants, phosphazenes, hexachlorocyclotriphosphazatriene, phenyltriphosphonitriles, cyclotriphosphazatrienes, butylamine
0108-7681
321-329
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Bartlett, S
a8a92aa3-0321-44b9-af34-8ad47cc95cd8
Davies, D.
b08c4b54-6246-4c36-bcb7-a78313526985
Ibisoglu, H.
d02665c2-a86b-4013-b6f9-48902447e2f7
Shaw, R.
525a62b3-df9a-40fd-8b01-cca1c77b5a5d
Kilic, A.
1406287f-d0aa-4211-b97a-1853ec5ee5b1
Un, I.
c0f90dc4-7da4-40c9-ac47-e6b8ce96468a
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Bartlett, S
a8a92aa3-0321-44b9-af34-8ad47cc95cd8
Davies, D.
b08c4b54-6246-4c36-bcb7-a78313526985
Ibisoglu, H.
d02665c2-a86b-4013-b6f9-48902447e2f7
Shaw, R.
525a62b3-df9a-40fd-8b01-cca1c77b5a5d
Kilic, A.
1406287f-d0aa-4211-b97a-1853ec5ee5b1
Un, I.
c0f90dc4-7da4-40c9-ac47-e6b8ce96468a

Coles, Simon J., Hursthouse, Michael B., Bartlett, S, Davies, D., Ibisoglu, H., Shaw, R., Kilic, A. and Un, I. (2006) Structural investigations of phosphorus-nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6 - n)(NHBut)n derivatives. Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials, 62 (2), 321-329. (doi:10.1107/S0108768106000851).

Record type: Article

Abstract

A series of compounds of the N3P3Cl(6 - n)(NHBut)n family (where n = 0, 1, 2, 4 and 6) are presented, and their molecular parameters are related to trends in physical properties, which provides insight into a potential reaction mechanism for nucleophilic substitution. The crystal structures of N3P3Cl5(NHBut) and N3P3Cl2(NHBut)4 have been determined at 120 K, and those of N3P3Cl6 and N3P3Cl4(NHBut)2 have been redetermined at 120 K. These are compared with the known structure of N3P3(NHBut)6 studied at 150 K. Trends in molecular parameters [phosphazene ring, P-Cl and P-N(HBut) distances, PCl2 angles, and endo- and exocyclic phosphazene ring parameters] across the series are observed. Hydrogen-bonding motifs are identified, characterized and compared. Both the molecular and the hydrogen-bonding parameters are related to the electron distribution in bonds and the derived basicities of the cyclophosphazene series of compounds. These findings provide evidence for a proposed mechanism for nucleophilic substitution at a phosphorus site bearing a PCl(NHBut) group

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Published date: April 2006
Keywords: x-ray crystallography, crystal-structure, cl33p3n3 compounds, molecular-parameters, basicity constants, phosphazenes, hexachlorocyclotriphosphazatriene, phenyltriphosphonitriles, cyclotriphosphazatrienes, butylamine

Identifiers

Local EPrints ID: 150701
URI: http://eprints.soton.ac.uk/id/eprint/150701
ISSN: 0108-7681
PURE UUID: 44225788-fcd4-43bd-9ec3-309a574a04c7
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 22 Jun 2010 08:41
Last modified: 14 Mar 2024 02:43

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Contributors

Author: Simon J. Coles ORCID iD
Author: S Bartlett
Author: D. Davies
Author: H. Ibisoglu
Author: R. Shaw
Author: A. Kilic
Author: I. Un

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