The Hexaazidogermanate(IV) Ion: Syntheses, Structures, and Reactions

Ideal S2 symmetry is shown by the [Ge(N3)6]2− ion (1) in the crystal lattice of the [N(PPh3)2] salt, whereas density functional calculations predict an S6-symmetric minimum structure for 1. Short interionic Na−N contacts lead to a reduction of the symmetry of the anion to C1 in crystalline [Na2(thf)3(Et2O)][Ge(N3)6], the product of the reaction of GeCl4 with NaN3. With Lewis bases, 1 reacts to give derivatives of the long sought after tetraazide Ge(N3)4 (2; LL=2,2′-bipyridine, 1,10-phenanthroline).