A phosphorus-31 nuclear magnetic resonance study of amino-derivatives of the chlorocyclophosphazenes, N3P3Cl6 and N4P4Cl8

Abstract

The proton decoupled ³¹P n.m.r. spectra of an extensive series of primary and secondary amine derivatives of N₃P₃Cl₆ and N₄P₄Cl₈ have been recorded and analysed. ¹H-{³¹P} INDOR studies show that P–N–P coupling constants for cis-N₃P₃Cl₃(NMe₂)₃, N₃P₃(NMe₂)₆, and N₄P₄(NMe₂)₈ are positive. Trends in ³¹P chemical shifts and P–N–P coupling constants are discussed and compared with similar data for chloro(phenyl)- and amino(phenyl)-cyclophosphazenes. The appearance of ‘virtual coupling’ effects in the ¹H spectra of some of these derivatives and the origins of broadening effects in the ³¹P spectra are discussed.