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Structural investigations of phosphorus-nitrogen compounds. 4. Steric and electronic effects in dibenzylamino derivatives of hexachlorocyclotriphosphazatriene and 4,4,6,6-tetrachloro-2,2-diphenylcyclotriphosphazatriene

Record type: Article

A systematic study is presented on the products of aminolysis of N3P3Cl6 (1) and N3P3Ph2Cl4 (4) with dibenzylamine. Two series of mono- and disubstituted derivatives of compounds (1) and (4), namely N3P3Cl5 [N(CH2Ph)(2)] (2) and N3P3Cl4 [N(CH2Ph)(2)](2) (3) and N3P3Ph2Cl3 [N(CH2Ph)(2)] (5) and N3P3Ph2Cl2 [N(CH2Ph)(2)](2) (6) [where (2), (3), (5) and (6) are new structures], are investigated in order to determine whether steric or electronic effects prevail in the formation of dibenzylamino-substituted cyclophosphazenes. The influence of an electron-releasing group (i.e. phenyl) on the stereochemistry and degree of substitution of the product is analysed by comparison of the above two series. The difference in unsymmetrically substituted endocyclic P-N bond lengths, Delta, is used as a measure of the degree of the electronic contribution, in combination with basicity constants, to quantify the degree of the electron-releasing capacity of the R group. In order to compare geminal versus non-geminal substitution, a difunctional secondary amine was used to form the compound N3P3Cl4 [NMe(CH2)(3) NMe] (7) (a reinvestigation) for inclusion in this study. It is shown that electron-releasing groups have a greater effect on the lengthening of P-Cl bonds as opposed to endocyclic P-N bonds and that this effect is greater in the non-geminal PRCl case than for geminal PCl2. However, steric effects are shown to be dominant in the reactions of dibenzylamine with N3P3 derivatives, with a disposition to a trans stereochemistry in bisdibenzylamino derivatives.

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Citation

Besli, S., Coles, S. J., Davies, D. B., Hursthouse, M. B., Kilic, A., Mayer, T. A., Shaw, R. A. and Uslu, A. (2002) Structural investigations of phosphorus-nitrogen compounds. 4. Steric and electronic effects in dibenzylamino derivatives of hexachlorocyclotriphosphazatriene and 4,4,6,6-tetrachloro-2,2-diphenylcyclotriphosphazatriene Acta Crystallographica Section B - Structural Science, 58, pp. 545-552. (doi:10.1107/S0108768102003816).

More information

Published date: 1 June 2002
Keywords: crystal, products, bond

Identifiers

Local EPrints ID: 19675
URI: http://eprints.soton.ac.uk/id/eprint/19675
PURE UUID: cfd3d81e-95f8-439c-b185-63285d459a1c
ORCID for S. J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 16 Feb 2006
Last modified: 17 Jul 2017 16:30

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Contributors

Author: S. Besli
Author: S. J. Coles ORCID iD
Author: D. B. Davies
Author: A. Kilic
Author: T. A. Mayer
Author: R. A. Shaw
Author: A. Uslu

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