Group 14 metal complexes of heavy chalcogen-centered anions, M[((TePPr2)-Pr-i)(2)N](2) (5, M = Sn: 6, M = Pb) and M((TePPr2NPPr2Se)-Pr-i-Pr-i)(2) (7, M = Sn: 8, M = Pb), were synthesized in 64-89% yields by metathesis of alkali-metal salts of the ligands with group 14 metal dihalides. Crystallographic characterization of the complexes revealed that 5, 6, and 8 engage in metal ... chalcogen secondary bonds to generate dimers. whereas 7 is monomeric in the solid state. Multinuclear (H-1, P-31, Se-77, and Te-125) solution NMR data for these homoleptic complexes evinced dynamic behavior leading to the equivalence of the two ligand environments. The Pb-II complex 6was utilized as a single-source precursor to mi,,rometer-scale lead telluride particles via two divergent techniques: aerosol-assisted chemical vapordeposition of the cDmplex in THF/CH2Cl2 solution onto glass substrates yielded rectangular prisms, while solution injection of 6 in trin-oclylphosphine onto Si/SiO2(100) substrates heated to 200-220 degrees C resulted in the formation of wires. PXRD and EDX analysis of the products confirmed the phase purity of the PbTe materials.