The lithium reagent [(LiTePPr2NPPr2)-Pr-i-Pr-i] undergoes metathetical reactions with group 11 chlorides to give the complexes {M((TePPr2NPPr2)-Pr-i-Pr-i)}(3) (6: M = Cu; 7: M = Ag) and (Ph3P)Au((TePPr2NPPr2)-Pr-i-Pr-i) (8) as yellow crystalline solids. These new complexes were characterized by single crystal X-ray diffraction and multinuclear NMR spectroscopy. The tellurium atoms in the trimeric complexes 6 and 7 occupy bridging positions to give a Cu3Te3 ring in a twist-boat conformation with short M center dot center dot center dot M contacts (M = Cu, Ag). Variable temperature P-31 NMR and ESI-MS spectra for 6 and 7 give evidence for the formation of several oligomers in tetrahydrofuran solution. The reactions of 6 with dioxygen (or Me3NO), elemental sulfur, or red selenium generate the chalcogen-insertion products {Cu((TePPr2NPPr2E)-Pr-i-Pr-i)}(3) (9: E = O; 10: E = S; 11: E = Se), which were also structurally characterized by single crystal X-ray diffraction and multinuclear NMR spectroscopy. The lighter chalcogens are two-coordinate while the tellurium centers occupy bridging positions in the trimeric complexes 9-11 giving rise to Cu3Te3 rings in a chairlike conformation.