Octahedral monodithiolene complexes of iron: characterization of S,S'-coordinated dithiolate(1-) pi radical monoanions: a spectroscopic and density functional theoretical investigation.

The reaction of cis-[Fe(III)(cyclam)Cl(2)]Cl with 1 equiv of sodium N-diethyldithiocarbamate, toluene-3,4-dithiolate, and maleonitriledithiolate in methanol in the presence of triethylamine afforded the cations Fe(III)(cyclam)(Et(2)dtc) (1), Fe(III)(cyclam)(tdt) (2), and Fe(III)(cyclam)(mnt) (3), which were isolated as triflate, hexafluorophosphate, and tetrafluoroborate salt, respectively, using sodium triflate, potassium hexafluorophosphate, or sodium tetrafluoroborate as the source for the counteranion. Complexes 1, 2, and 3 possess an S = (1)/(2) ground state (low-spin ferric d(5)). These salts were characterized by X-ray crystallography, UV-vis, Mössbauer, and electron paramagnetic resonance spectroscopies. Cyclic voltammetry revealed that 2 and 3 are reversibly one-electron-reduced, generating neutral 2(red) and 3(red), respectively, and one-electron-oxidized, generating dicationic 2(ox) and 3(ox), respectively. Fe and S K-edge X-ray absorption spectroscopy (XAS) revealed that 2 (S = (1)/(2)) and 2(ox) (S = 0) possess a low-spin ferric ion. Complexes 2 and 3 are S,S'-coordinated to a closed-shell dithiolate(2-) ligand, whereas 2(ox) and 3(ox) consist of a low-spin ferric ion antiferromagnetically coupled to a dithiolate(1-) pi radical ligand. They are singlet diradicals Fe(III)(cyclam)(dithiolate(*)). The analysis of the sulfur K pre-edge transitions reveals significant multiplet effects in the spectra of 2 and 2(ox), which provide rare experimental evidence for a singlet diradical description for 2(ox). Mössbauer spectroscopy on frozen solutions of 2(red) clearly show the presence of a high-spin ferrous ion (S = 2). The experimentally established electronic structures of the three members of the electron transfer series Fe(cyclam)(dithiolate) have been verified by broken symmetry density functional theoretical calculations, which have been calibrated against the experiment by calculating XAS and Mössbauer spectra.