Bridged cyclophosphazenes resulting from deprotonation reactions of cyclotriphophazenes bearing a P–NH group

Beşli, Serap, Coles, Simon J., Davies, David B., Kılıç, Adem and Shaw, Robert A. (2011) Bridged cyclophosphazenes resulting from deprotonation reactions of cyclotriphophazenes bearing a P–NH group. Dalton Transactions, 40 (19), 5307-5315. (doi:10.1039/c1dt10073d).

Abstract

Cyclotriphosphazene derivatives containing a P-NHR group in the side-chain react in the presence of a strong base to form stable intermolecular bridged products. Reaction of sodium hydride with mono-spiro cyclophosphazene derivatives having a P-NH group, N3P3Cl4[O(CH2)(3)NH], (1a) or N3P3Cl4[CH3N(CH2)(3)NH], (1b) leads to formation of bis-cyclophosphazenes bridged with an eight-membered cyclophosphazene ring in an ansa arrangement (2a, 2b) whereas reaction of sodium hydride with mono-amino cyclophosphazene derivatives [N3P3Cl5(NHR), R = n-hexyl, 3a; i-Pr, 3b; Ph, 3c] give bis-cyclophosphazenes bridged with a four-membered cyclophosphazane ring in a spiro arrangement (4a-c). In the latter reaction P-O-P bridged compounds (5a-c) were also obtained as a result of hydrolysis reactions associated with the amount of moisture in the solvent tetrahydrofuran. In addition, it was found that reaction of a mixture of cyclotriphosphazene with either mono spiro compound, (1a) or (1b), in the presence of sodium hydride lead to formation of the first examples of asymmetrically-bridged cyclophosphazenes (6a-b).

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Contributors

Author: Simon J. Coles

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