Application of Lever’s EL Parameter Scale toward Fe(II)/Fe(III) versus Pc(2-)/Pc(1-) Oxidation Process Crossover Point in Axially Coordinated Iron(II) Phthalocyanine Complexes
| Autor: | Karl M. Kadish, Victor N. Nemykin, W. Ryan Osterloh, Dustin E. Nevonen, Laurel A Harrison, Laura S. Ferch, Benjamin S Marx |
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| Rok vydání: | 2021 |
| Předmět: |
010405 organic chemistry
Ligand 010402 general chemistry Electrochemistry 01 natural sciences 0104 chemical sciences Inorganic Chemistry Metal chemistry.chemical_compound Crystallography chemistry visual_art Pyridine Imidazolate Phthalocyanine visual_art.visual_art_medium Imidazole Density functional theory Physical and Theoretical Chemistry |
| Zdroj: | Inorganic Chemistry. 60:16626-16644 |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | The electronic structures and, particularly, the nature of the HOMO in a series of PcFeL2, PcFeL'L″, and [PcFeX2]2- complexes (Pc = phthalocyaninato(2-) ligand; L = NH3, n-BuNH2, imidazole (Im), pyridine (Py), PMe3, PBu3, t-BuNC, P(OBu)3, and DMSO; L' = CO; L″ = NH3 or n-BuNH2; X = NCO-, NCS-, CN-, imidazolate (Im-), or 1,2,4-triazolate(Tz-)) were probed by electrochemical, spectroelectrochemical, and chemical oxidation as well as theoretical (density functional theory, DFT) studies. In general, energies of the metal-centered occupied orbitals in various six-coordinate iron phthalocyanine complexes correlate well with Lever Electrochemical Parameter EL and intercross the phthalocyanine-centered a1u orbital in several compounds with moderate-to-strong π-accepting axial ligands. In these cases, an oxidation of the phthalocyanine macrocycle (Pc(2-)/Pc(1-)) rather than the central metal ion (Fe(II)/Fe(III)) was theoretically predicted and experimentally confirmed. |
| Databáze: | OpenAIRE |
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