The novel pyrazolyl-based ligands 3, 5-Me2pz (CH2) 2NH (CH2) 2NH (CH2) 2NH2 (1) and pz*(CH2) 2NH-Gly-CH2STrit (pz*= pz (8), 3, 5-Me2pz (9), 4-(EtOOC) CH2-3, 5-Me2pz (10)) were synthesized, and their suitability to stabilize Re (V) oxocomplexes was evaluated using different starting materials, namely (NBu4)[ReOCl4],[ReOCl3 (PPh3) 2] and trans-[ReO2 (py) 4] Cl. Compound 1 reacts with trans-[ReO2 (py) 4] Cl yielding the cationic compound [ReO ...