24-N,N'-disubstituted 1,3,5-triazapentadienyl ligands as their lithium salts [Li{(N(R)C(R'))(2)N)](2) [where R = SiMe3 here and hereafter and R' = dimethylamino (1) or 1-piperidino (2)] were synthesized via the reactions of LiN(SiMe3)(2) with 2 equiv of the alpha-hydrogen-free carbonitrile dimethylcyanamide or 1-piperdinecarbonitrile and used in the isolation of the two-coordinate copper(l) complexes [Cu{(N(R)C(R'))(2)N}](2) [R' = dimethylamino (3) and 1-piperidino (4)]. Complex 2 features a twisted W-shaped ligand backbone in the solid state. Complexes 3 and 4 show an unusual 12-membered ring dinuclear copper(1) triazapentadienyl and a less expressed ability to form a stable delocalized triazapentadienyl system.