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Structural investigations of phosphorus-nitrogen compounds. 5. Relationships between molecular parameters of 2,2-diphenyl-4,6-cis-oxytetra(ethyleneoxy)-4,6-R-2-cyclotriphosphazatrie nes (R = Cl, OCH2CF3, OPh, OMe, NHPh, NHBut) and substituent basicity constants

Structural investigations of phosphorus-nitrogen compounds. 5. Relationships between molecular parameters of 2,2-diphenyl-4,6-cis-oxytetra(ethyleneoxy)-4,6-R-2-cyclotriphosphazatrie nes (R = Cl, OCH2CF3, OPh, OMe, NHPh, NHBut) and substituent basicity constants
Structural investigations of phosphorus-nitrogen compounds. 5. Relationships between molecular parameters of 2,2-diphenyl-4,6-cis-oxytetra(ethyleneoxy)-4,6-R-2-cyclotriphosphazatrie nes (R = Cl, OCH2CF3, OPh, OMe, NHPh, NHBut) and substituent basicity constants
A systematic study of the products of nucleophilic substitution reactions of cis-ansa N3P3Ph2[O(CH2CH2O)(4)]Cl-2 (3) is reported. These reactions give a number of new structures with the general formula N3P3Ph2[O(CH2CH2O)(4)]R-2 [where R=OCH2CF3 (4), OPh (5), OMe (6), NHPh (7.H2O), NHBut ( 8)]. A comparison has been made between the sum of the substituent basicity constants, Sigmaalpha(R), that are obtained in nitrobenzene solution and eight molecular parameters of the N3P3 ring [the P-N bond lengths a, b, c; the internal bond angles alpha, beta, gamma, delta; and the difference between the bond lengths a and b, Delta(P-N)]. It is found that the systematic changes in the molecular parameters of (3)-(8) are in line with changes in alpha(R) values. This result implies the similarity in relative electron-releasing capacity of substituents R in the solid state and in solution.
crystal-structure, derivatives, complex, ether
1067-1073
Besli, S.
fec9f1df-e8c0-4984-a2c9-e1161447a7d2
Coles, S. J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, D. B.
ce9eed8e-659b-4fca-95e4-acaa6befb08b
Hursthouse, M. B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kilic, A.
1406287f-d0aa-4211-b97a-1853ec5ee5b1
Mayer, T. A.
7745fac9-3d30-431e-a045-acfdf1ce7000
Shaw, R. A.
0f2133b1-7aac-4d36-a9dc-75630c4a78a0
Besli, S.
fec9f1df-e8c0-4984-a2c9-e1161447a7d2
Coles, S. J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, D. B.
ce9eed8e-659b-4fca-95e4-acaa6befb08b
Hursthouse, M. B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kilic, A.
1406287f-d0aa-4211-b97a-1853ec5ee5b1
Mayer, T. A.
7745fac9-3d30-431e-a045-acfdf1ce7000
Shaw, R. A.
0f2133b1-7aac-4d36-a9dc-75630c4a78a0

Besli, S., Coles, S. J., Davies, D. B., Hursthouse, M. B., Kilic, A., Mayer, T. A. and Shaw, R. A. (2002) Structural investigations of phosphorus-nitrogen compounds. 5. Relationships between molecular parameters of 2,2-diphenyl-4,6-cis-oxytetra(ethyleneoxy)-4,6-R-2-cyclotriphosphazatrie nes (R = Cl, OCH2CF3, OPh, OMe, NHPh, NHBut) and substituent basicity constants. Acta Crystallographica Section B: Structural Science, 58, 1067-1073. (doi:10.1107/S0108768102018608).

Record type: Article

Abstract

A systematic study of the products of nucleophilic substitution reactions of cis-ansa N3P3Ph2[O(CH2CH2O)(4)]Cl-2 (3) is reported. These reactions give a number of new structures with the general formula N3P3Ph2[O(CH2CH2O)(4)]R-2 [where R=OCH2CF3 (4), OPh (5), OMe (6), NHPh (7.H2O), NHBut ( 8)]. A comparison has been made between the sum of the substituent basicity constants, Sigmaalpha(R), that are obtained in nitrobenzene solution and eight molecular parameters of the N3P3 ring [the P-N bond lengths a, b, c; the internal bond angles alpha, beta, gamma, delta; and the difference between the bond lengths a and b, Delta(P-N)]. It is found that the systematic changes in the molecular parameters of (3)-(8) are in line with changes in alpha(R) values. This result implies the similarity in relative electron-releasing capacity of substituents R in the solid state and in solution.

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Published date: 1 December 2002
Keywords: crystal-structure, derivatives, complex, ether

Identifiers

Local EPrints ID: 19674
URI: http://eprints.soton.ac.uk/id/eprint/19674
PURE UUID: 6961decb-8ddd-4549-bcaa-db7ea77ac947
ORCID for S. J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 16 Feb 2006
Last modified: 18 Feb 2021 16:52

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