96502-36-2Relevant articles and documents
Electrochemistry and spectroelectrochemistry of σ-bonded aryliron porphyrins. 3. Synthesis and characterization of high, low, and variable spin state five-coordinate σ-bonded aryl- And perfluoroaryliron(III) complexes
Guilard,Boisselier-Cocolios,Tabard,Cocolios,Simonet,Kadish
, p. 2509 - 2520 (2008/10/08)
The syntheses of 10 novel high- and low-spin σ-bonded aryliron(III) porphyrins are reported and their electrochemical behaviors characterized in benzonitrile containing 0.1 M tetrabutylammonium hexafluorophosphate as supporting electrolyte. Each neutral complex was also characterized by 1H NMR, ESR, IR, and UV-visible spectroscopy, and on the basis of these data, the spin state of the Fe(III) was assigned as either high-spin S = 5/2 or low-spin S = 1/2. σ-Bonded Fe(III) porphyrins have generally been described as low-spin species, and an assignment of high-spin Fe(III) at room temperature has never been reported in the literature. Comparisons are made between the redox reactivity and physicochemical properties of these new complexes and results already reported in the literature for low-spin σ-bonded phenyl- and alkyliron(III) porphyrins. Finally, it is demonstrated how the spin state of the σ-bonded aryliron(III) porphyrins and the chemical and electrochemical reactivity can be varied as a function of the porphyrin ring basicity and/or the ligand field strength of the σ-bonded ligand.
