A cis-directing effect towards diols by an exocyclic P-NHR moiety in cyclotriphosphazenes

Beşli, Serap, Coles, Simon J., Davies, David B., Kılıç, Adem, Okutan, Elif, Shaw, Robert A., Tanrıverdi, Esra and Çiftçi, Gönül Yenilmez (2009) A cis-directing effect towards diols by an exocyclic P-NHR moiety in cyclotriphosphazenes. Inorganic Chemistry Communications, 12 (8), 773-777. (doi:10.1016/j.inoche.2009.06.014).

Abstract

Cyclophosphazenes containing the P-NHR moiety in an exocyclic spiro ring, N(3)P(3)Cl(4)[NH(CH(2))(3)O], (1), and N(3)P(3)Cl(4)[NH(CH(2))(3)NMe], (2). were used to investigate a possible directing effect of the P-NHR moiety oil the formation of products in the nucleophilic substitution reactions with diols Such as tetraethyleneglycol, 1,3-propanediol and 2,2-dimetliyl-1,3-propanediol. The (31)P NMR spectra of the reaction Mixtures showed that only one kind of ansa product is formed in each of these reactions. X-ray crystallographic studies of the ansa products [(4a), (5a), (6a) and (7a)] have provided definitive proof of the cis-directing effect of the P-NHR moiety in cyclotriphosphazenes. It is likely that hydrogen-bond interaction between the incoming nucleophile and the P-NHR moiety of the reactant accounts for the preference for products with the substituents cis to the NH group.

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Contributors

Author: Simon J. Coles

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