A comprehensive investigation of reactions of alkali-metal derivatives of the ditelluro dianion [TePV((NBu)-Bu-t)(mu-(NBu)-Bu-t)](2)(2-) (L2-, E = Te) with p-block element halides produced a series of novel heterocycles incorporating (P2N2)-N-V rings, tellurium, and group 13-16 elements. The dianion engages in Te,Te'-chelation to the metal center in Ph2Ge and R2Sn (R = Bu-t, Bu-n, Ph) derivatives; similar behavior was noted for group 14 derivatives of L2- (E = S, Se). In the case of group 13 trihalides MCl3 (M = Ga, In), neutral spirocyclic complexes (L)M[(NBu)-Bu-t(Te)P-v(mu-(NBu)-Bu-t)(2)(PN)-N-III(H)Bu-t)] (M = Ga, In) comprised of a Te,Te'-chelated ligand L2- and a N,Te-bonded ligand resulting from loss of Te and monoprotonation were obtained. In reactions with RPCl2 (R = Bu-t, Ad, (Pr2N)-Pr-i) a significant difference was observed between Se- and S-containing systems. In the former case, Se,Se'-chelated derivatives were formed in high yields, whereas the N,S-chelated isomers predominated for sulfur. All complexes were characterized by multinudear (H-1, P-31, Se-77, Sn-119, and Te-123) NMR spectroscopy; this technique was especially useful in the analysis of the mixture of (L) (Se) and (L)(SeSe) obtained from the reaction of Se2Cl2 with L2- (E = Te). Single-crystal X-ray structures were obtained for the spirocydic In complex (9), (L)GePh2 (E = Te, 10), (L)(SnBu2)-Bu-t = Te, 12a); E = Se, 12aSe, E = S, 12aS) and (L)(mu-SeSe) (E = Te, 16).