From the interaction of imidazole-type ligand L (L=imidazole (im), 1-methylimidazole (1-meim), 2-methylimidazole (2-meim), 4-methylimidazole (4-meim), benzimidazole (bzim), 1-benzylimidazole (bnim)) with [Cu(N3)(PPh3)2]2 the new mononuclear [Cu(N3)(PPh3)2(L)] and dinuclear [Cu2(N3)2(PPh3)3(L)] species have been obtained. Chelating bidentate ligands (L2=2,2-bipyridyl (bipy), 1,10-phenanthroline (phen) or 2,9-dimethyl-1,10-phenanthroline (cupr)) react with [M(N3)(PPh3)2]2 (M=Cu or Ag) yielding [M(N3)(PPh3)(L2)]. The S-donors 1-methyl-2-imidazol-2(3H)-thione (Hmimt), 2-benzothiazolethiol (Hbtt) and 2-pyridinethiol (Hpyt) react with [Cu(N3)(PPh3)2]2 in ethanol undergoing deprotonation and yielding [Cu(mimt)(Ph3P)]n, [Cu(btt)]n and [Cu(pyt)]n, respectively. On the contrary, Hmimt and imidazoline-2(1,3H)thione (Himt) react in diethyl ether with [Cu(N3)(PPh3)2]2 yielding [Cu(N3)(Hmimt)3] and [Cu(N3)(PPh3)(Himt)], respectively. P(o-tolyl)3 is able to displace the less basic phosphine PPh3 from [Cu(N3)(PPh3)(cupr)] yielding the complex [Cu(N3){P(o-tolyl)3}(cupr)]. 1,3-Bis(diphenylphosphino)propane (dppp) reacts with [Cu(N3)(PPh3)(cupr)] yielding the complex [Cu2(N3)2(dppp)3]. [Cu(N3)(PPh3)2(im)] and [Cu(N3)(PPh3)(phen)] react with CS2 in benzene, in presence of excess of PPh3 forming [Cu(SCN)(PPh3)2] and [Cu(tz)(PPh3)(phen)] (Htz=4-thia-1,2,3-triazole-5-thione), respectively. [Ag(N3)(PPh3)(cupr)] reacts slowly with excess of CS2 in diethyl ether giving [Ag(tz)(cupr)], whereas the same reaction in benzene in excess of PPh3 yields immediately [Ag(SCN)(PPh3)2]. From the reaction of [Ag(N3)(PPh3)(cupr)] with cyCN the complex [Ag(N3)(cyCN)(PPh3)(cupr)] formed. All derivatives were characterized by IR and far-IR data, conductivity, 1H NMR and in some cases also with 31P{1H} NMR and molecular weight measurements.