Phenalene-phosphazene complexes: effect of exocyclic charge densities on the cyclotriphosphazene ring system

The synthesis and properties of a new series of 1,9-diamino-substituted phenalene complexes of the cyclotriphosphazene ring system is described. One of the compounds is shown to be amphoteric, and this behavior allows an examination of the response of the phosphazene linkage to variations in exocyclic charge density at the spiro center in a plane perpendicular to the cyclotriphosphazene ring system. ^(31)P NMR spectroscopy indicates that substituent lone pairs with this orientation are not effective in long-range delocalization within the phosphazene linkage (in accord with our theoretical model of spiro delocalization). An X-ray crystal structure of one compound (7) identifies the presence of clathrated molecules of chloroform together with doubly hydrogen-bonded pairs of the phenalene-phosphazene complexes in the lattice. Crystal data for 7 (C_(13)H_8Cl_4N_5P_3•CHCl_3): monoclinic space group P2_1/c, a = 12.401 (4) Å, b = 28.404 (6) Å, c = 12.962 (3) Å, β = 91.76 (2)°, V = 4564 (2) Å^3, Z = 8, R = 0.050 for 4525 reflections