Reaction of cis-[FeIII(cyclam)Cl2]Cl in acidic H2O/CH3OH or CH3CN/H2O mixtures with NaN3 at 50 °C produced upon addition of NaClO4 or NaPF6 the complex trans-[FeIII(cyclam)(N3)2]ClO4 (1a) or the hexafluorophosphate salt 1b, whereas at −18 °C the same reaction produced cis-[FeIII(cyclam)(N3)2](ClO4) (2) (cyclam = 1,4,8,11-tetraazacyclotetradecane). The crystal structures of 1b and 2 were determined by single-crystal X-ray crystallography. Complexes 1a, b, contain a low-spin (S = 1/2) and 2, a high-spin ferric ion (S = 5/2) as was established by variable-temperature magnetic susceptibility measurements and Mossbauer and X-band EPR spectroscopy. The low-spin trans-[(cyclam)FeII(N3)2] and high-spin cis-[(cyclam)FeII(N3)2] species were generated electrochemically in CH3CN solution and were characterized by Mossbauer spectroscopy. Photolysis of 1a in CH3CN at −35 °C and 20 °C with a Hg immersion lamp generated within 15 min a yellow solution. EPR and Mossbauer spectra show that a single high-valent species with...