The cyanamides Me2NCN (la), OC4H8NCN (1b), and PhC(=O)N(H)CN (1c) and the conventional nitriles PhCN (1d) and EtCN (1e) react with 1 equiv of each of the amidoximes R'C(=NOH)NH2 (R' = Me (2a), Ph (2b)) in the presence of 1 equiv of ZnCl2 producing the complexes [ZnCl2(HN=C(R)ON=C(R')NH2}] (R/R' = NMe2/Me (3a), NMe2/Ph (3b), NC4H8O/Me (3c), NC4H8O/Ph (3d), N(H)C(=0)Ph/Me (3e), N(H)C(=O)Ph/Ph (3f), Ph/Me (3g), Ph/Ph (3h), Et/Ph (3j)) with the chelate ligands originating from the previously unreported zinc(II)-mediated nitrile-amidoxime coupling. Addition of 1 equiv of p-TolSO(3)H to any of one 3a-h, 3j results in the ligand liberation and formation of the iminium salts [H2N= C(R)ON=C(R')NH2}(p-TolSO(3)) ([4a-n(p-TolSO(3))), which then at 20-65 degrees C spontaneously transform to 1,2,4-oxadiazoles (5a-j). As a side reaction, cyanamide derived species [4a-f](p-TolSO(3)) undergo Tiemann rearrangement to produce the substituted ureas R'NHC(=O)NH2 (R' = Me (6a), Ph (6b)) and RC(=O)NH2 (R = NMe2 (6c), NC4H8O (6d), N(H)C(= O)Ph (6e)), whereas phenyl and ethyl cyanide derivatives besides their transformation to the oxadiazoles undergo hydrolysis to the parent amidoxime R'C(=NOH)NH2 (R' = Me (2a), Ph (2b)) and the carboxamides RC(=O)NH2 (R = Ph (6f), Et (6g)). All new obtained compounds were characterized by HRESI-MS, IR, ATR-FTIR, H-1 NMR, CP-MAS TOSS C-13 NMR, elemental analyses (C, H, N), and single crystal X-ray diffraction for seven species (3a-e, [4b](p-TolSO(3)), and [4d}(p-TolSO(3))). Two previously unknown heterocycles Sc and Se were isolated and characterized by elemental analyses (C, H, N), HRESI-MS, IR, H-1 and C-13{H-1} NMR. The observed conversion of [4a-j](p-TolSO(3)) to the 1,2,4-oxadiazoles uncovers the mechanism of the previously reported Htassisted generation of these heterocycles (Augustine; et al. J. Org. Chem. 2009, 74, 5640).