Sterically demanding triazapentadiene [N{(C3F7)C(Dipp)N}(2)]H affords the isolation of thermally stable, two- and three-coordinate silver complexes. The free ligand [N{(C3F7)C(Dipp)N}(2)]H has a W-shaped ligand backbone in the solid state. [N{(C3F7)C(Dipp)N}(2)]H reacts with silver(l) oxide in acetonitrile leading to CH3CNAg[NT(C3F7)C(Dipp)N}(2)], It features a two-coordinate silver center and a K'-coordinated triazapentaclienyl ligand. This silver acetonitrile complex serves as an excellent precursor to obtain thermally stable, silver isocyanide t-BuNCAg[N{(C3F7)C(Dipp)N}(2)] and silver phosphine [N{(C3F7)C(Dipp)N}(2)]AgPPh3 adducts. IR spectroscopic data for the silver(l)isocyanide t-BuNCAg[N{(C3F7)C(Dipp)N}(2)] shows VCN at 2219 cm(-1). The silver ion coordinates to the triazapentaclienyl ligand via the central nitrogen atom. The silver PPh3 adduct, [N{(C3F7)C(Dipp)N}(2)]AgPPh3, was synthesized by treating CH3CNAg[N{(C3F7)C(Dipp)N}(2)] with PPh3. It displays relatively large Ag-P coupling in the P-31 NMR spectrum. The triazapentadienyl ligand in [N{(C3F7)C(Dipp)N}(2)]AgPPh3 acts as a chelating kappa(2)-donor. The Ag-P bond is relatively short (2.3487(10) Angstrom).