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


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).

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Description/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.

Item Type: Article
Related URLs:
Keywords: crystal-structure, derivatives, complex, ether
Subjects: Q Science
Q Science > QD Chemistry
Divisions: University Structure - Pre August 2011 > School of Chemistry
ePrint ID: 19674
Date Deposited: 16 Feb 2006
Last Modified: 27 Mar 2014 18:09
URI: http://eprints.soton.ac.uk/id/eprint/19674

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