Kinetic studies of the reactions of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene with t-butylamine

Krishnamurthy, Setharampattu S and Sundaram, Ponnuswamy M (1982) Kinetic studies of the reactions of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene with t-butylamine. In: Dalton Transactions (1). pp. 67-71.

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Abstract

The rates of the reactions of hexachlorocyclotriphosphazene (N3P3Cl6) and octachlorocyclotetraphosphazene (N4P4Cl8) with t-butylamine in methyl cyanide were determined at three temperatures in the range 273–308 K. The reaction of N3P3Cl6 was also studied in tetrahydrofuran. Rigorous purification of the chlorophosphazenes and the solvents was essential to obtain reproducible results. An SN2(P) mechanism involving the formation of a five-co-ordinate phosphorus intermediate is in accord with the kinetic data. The greater reactivity of N4P4Cl8 compared to that of N3P3Cl6 arises entirely from the lowering of the enthalpy of activation. The effects of ring size and the solvent on the rates are discussed in terms of the activation parameters.

Item Type:	Journal Article
Publication:	Dalton Transactions
Publisher:	Royal Society of Chemistry
Additional Information:	Copyright of this article belongs to Royal Society of Chemistry.
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	31 Aug 2009 05:27
Last Modified:	19 Sep 2010 05:43
URI:	http://eprints.iisc.ac.in/id/eprint/22681

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