Mononuclear (Nitrido)iron(V) and (Oxo)iron(IV) Complexes via Photolysis of (cyclam-acetato)FeIII(N3)+ and Ozonolysis of (cyclam-acetato)FeIII(O3SCF3)+ in Water/Acetone Mixtures

Reaction of the monoanionic, pentacoordinate ligand lithium 1,4,8,11-tetraazacyclotetradecane-1-acetate, Li(cyclam-acetate), with FeCl3 yields, upon addition of KPF6, (cyclam-acetato)FeClPF6 (1) as a red microcrystalline solid. Addition of excess NaN3 prior to addition of KPF6 yields the azide derivative (cyclam-acetato)FeN3PF6 (2a) as orange microcrystals. The X-ray crystal structure of the azide derivative has been determined as the tetraphenylborate salt (2b). Reaction of 1 with silver triflate yields (cyclam-acetato)Fe(O3SCF3)PF6 (3), which partially dissociates triflate in nondried solvents to yield a mixture of triflate and aqua bound species. Each of the iron(III) derivatives is low-spin (d5, S = 1/2) as determined by variable-temperature magnetic susceptibility measurements, Mössbauer and EPR spectroscopy. The low-spin iron(II) (d6, S = 0) complexes 1red and 2ared have been prepared by electrochemical and chemical methods and have been characterized by Mössbauer spectroscopy. Photolysis of 2a at 419 nm in frozen acetonitrile yields a nearly colorless species in approximately 80% conversion with an isomer shift delta = -0.04 mm/s and a quadrupole splitting delta EQ = -1.67 mm/s. A spin-Hamiltonian analysis of the magnetic Mössbauer spectra is consistent with an FeV ion (d3, S = 3/2). The proposed (cyclam-acetato)FeV=N+ results from the photooxidation of 2a via heterolytic N-N cleavage of coordinated azide. Photolysis of 2a in acetonitrile solution at -35 degrees C (300 nm) or 20 degrees C (Hg immersion lamp) results primarily in photoreduction via homolytic Fe-Nazide cleavage yielding FeII (d,6 S = 0) with an isomer shift delta = 0.56 mm/s and quadrupole splitting delta EQ = 0.54 mm/s. A minor product containing high-valent iron is suggested by Mössbauer spectroscopy and is proposed to originate from ((cyclam-acetato)Fe)2(mu-N)2+ with a mixed-valent (FeIV(mu-N)FeIII))4+S = 1/2 core. Exposure of 3 to a stream of oxygen/ozone at low temperatures (-80 degrees C) in acetone/water results in a single oxidized product with an isomer shift delta = 0.01 mm/s and quadrupole splitting delta EQ = 1.37 mm/s. A spin-Hamiltonian analysis of the magnetic Mössbauer yields parameters similar to those of compound II of horseradish peroxidase which are consistent with an FeIV=O monomeric complex (S = 1).