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Structural investigations of phosphorus-nitrogen compounds. 6. Relationships between molecular parameters in per-X-substituted bridged spermine derivatives and basicity constants ??R of substituents

Structural investigations of phosphorus-nitrogen compounds. 6. Relationships between molecular parameters in per-X-substituted bridged spermine derivatives and basicity constants ??R of substituents
Structural investigations of phosphorus-nitrogen compounds. 6. Relationships between molecular parameters in per-X-substituted bridged spermine derivatives and basicity constants ??R of substituents
A systematic study is reported of the products of the nucleophilic substitution reactions of the spermine-bridged cyclotriphosphazene, [N3P3X4(NHCH2CH2CH2N)CH2CH2]2 [where X = Cl (2a)], to give a number of new structures [(2b)-(2g)] in which X = OPh, [spiro-O(CH2)3O]0.5, Ph, NHPh, NC4H8 and NHBut, respectively. A comparison has been made between the sum of the substituent basicity constants, ΣαR, obtained in nitrobenzene solution, and ten molecular parameters of the N3P3 ring (the internal bond angles α, β, γ, δ and θ, and the P-N bond lengths a, b, c, d and e) as well as the difference between the bond lengths a and b, Δ(P-N). It is found that the systematic change in molecular parameters of compounds (2a)-(2g) is in line with changes in αR values, indicating the similarity in relative electron-releasing capacity of substituents X in the solid state and in solution. It is also found that the effect on molecular parameters of (2a)-(2g) with two X substituents in PX2 groups is greater than that for one X substituent in P(OR)X groups in an analogous series of compounds observed previously [Besli et al. (2002). Acta Cryst. B58, 1067-1073].
0108-7681
739-747
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, D.B.
bf1a738f-6739-4e53-ad8b-f860b599f597
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kilic, A.
1406287f-d0aa-4211-b97a-1853ec5ee5b1
Mayer, T.A.
dd811782-43f3-469c-a475-f3e017da8358
Shaw, R.A.
2b5836d0-91f9-468a-b7fe-365beb0a4052
Ciftci, G.Y.
36c6f31c-8dc5-4f7b-9eaf-2985b0ec9f51
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, D.B.
bf1a738f-6739-4e53-ad8b-f860b599f597
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kilic, A.
1406287f-d0aa-4211-b97a-1853ec5ee5b1
Mayer, T.A.
dd811782-43f3-469c-a475-f3e017da8358
Shaw, R.A.
2b5836d0-91f9-468a-b7fe-365beb0a4052
Ciftci, G.Y.
36c6f31c-8dc5-4f7b-9eaf-2985b0ec9f51

Coles, S.J., Davies, D.B., Hursthouse, M.B., Kilic, A., Mayer, T.A., Shaw, R.A. and Ciftci, G.Y. (2004) Structural investigations of phosphorus-nitrogen compounds. 6. Relationships between molecular parameters in per-X-substituted bridged spermine derivatives and basicity constants ??R of substituents. Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials, 60 (6), 739-747. (doi:10.1107/S0108768104025947).

Record type: Article

Abstract

A systematic study is reported of the products of the nucleophilic substitution reactions of the spermine-bridged cyclotriphosphazene, [N3P3X4(NHCH2CH2CH2N)CH2CH2]2 [where X = Cl (2a)], to give a number of new structures [(2b)-(2g)] in which X = OPh, [spiro-O(CH2)3O]0.5, Ph, NHPh, NC4H8 and NHBut, respectively. A comparison has been made between the sum of the substituent basicity constants, ΣαR, obtained in nitrobenzene solution, and ten molecular parameters of the N3P3 ring (the internal bond angles α, β, γ, δ and θ, and the P-N bond lengths a, b, c, d and e) as well as the difference between the bond lengths a and b, Δ(P-N). It is found that the systematic change in molecular parameters of compounds (2a)-(2g) is in line with changes in αR values, indicating the similarity in relative electron-releasing capacity of substituents X in the solid state and in solution. It is also found that the effect on molecular parameters of (2a)-(2g) with two X substituents in PX2 groups is greater than that for one X substituent in P(OR)X groups in an analogous series of compounds observed previously [Besli et al. (2002). Acta Cryst. B58, 1067-1073].

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Published date: 2004

Identifiers

Local EPrints ID: 26998
URI: https://eprints.soton.ac.uk/id/eprint/26998
ISSN: 0108-7681
PURE UUID: 896e2d9e-ea86-44d7-80cb-78c8667ab2e0
ORCID for S.J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 25 Apr 2006
Last modified: 31 Jul 2018 00:34

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