Abstract
The chiral macrobicyclic tri-λ 5-phosphazenes formed by tripod–tripod coupling of tris(3-azidobenzyl)amines and 1,1,1-tris[(diphenylphosphino)methyl]methanes present helical topologies as a result of combining two propeller-shaped tripodal fragments with the same sense of twist. The introduction of a series of R piv substituents of increasing size at the pivotal carbon of the lower tert-butane fragment R piv–C(CH 2PPh 2) 3 causes a gradual decrease of the helicity in the lower propeller. This phenomenon is revealed in their CDCl 3 solution NMR spectra, and the activation energies for the racemization process of the tri-λ 5-phosphazenes were calculated by coalescence VT-NMR experiments.
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