BIROn - Birkbeck Institutional Research Online

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

Bartlett, S.W. and Coles, Simon J. and Davies, David B. and Hursthouse, Michael B. and Ibişoğlu, H. and Kiliç, A. and Shaw, Robert A. and Ün, İ. (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 62 (2), pp. 321-329. ISSN 0108-7681.

[img]
Preview
Text
davies374a.pdf

Download (1017Kb) | Preview
Official URL: http://dx.doi.org/10.1107/S0108768106000851

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 120K and those of N3P3Cl6 and N3P3Cl4(NHBut)2 have been re-determined at 120K. These are compared with the known structure of N3P3(NHBut)6 studied at 150K. Trends in molecular parameters (phosphazene ring, P-Cl & P-N(HBut) distances, PCl2 angles and endo- and exo-cyclic phosphazene ring parameters) across the series are observed. Hydrogen-bonding motifs are identified, characterised and compared. Both the molecular and 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) moiety.

Item Type: Article
Additional Information: The definitive version is available at www.blackwell-synergy.com
Keyword(s) / Subject(s): structure-property relationships, cyclophosphazenes, hydrogen bonding, structural systematics
School or Research Centre: Birkbeck Schools and Research Centres > School of Science > Biological Sciences
Depositing User: Sandra Plummer
Date Deposited: 07 Jun 2006
Last Modified: 17 Apr 2013 12:32
URI: http://eprints.bbk.ac.uk/id/eprint/374

Archive Staff Only (login required)

Edit/View Item Edit/View Item