PubMed · 5444469
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J A Hathaway, J J Sannella, D T Hunter. 1970. Thyroxine determination by continuous spectrophotometry.. https://doi.org/10.1093/ajcp%2F53.5.635
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The electronic structure, molecular structure, and electronic spectra of lanthanide(III) mono- and bisporphyrin complexes are investigated using a DFT/TDDFT method. These complexes include YbP(acac), YbP(2), [YbP(2)](+), YbHP(2), and [YbP(2)](-) (where P = porphine and acac = acetylacetonate). To shed some light on the origin of the out-of-plane displacement of Yb in YbP(acac), unligated model systems, namely, planar D(4h) and distorted C(4nu) YbP, were calculated. For comparison, the calculations were also extended to include the C and [Ce(IV)P(2) ](+) systems. Even without an axial ligand, the lanthanide atom lies considerably above the porphyrin plane; the distortion of the YbP molecular structure from a planar D(4h) to the nonplanar C(4nu) symmetry leads to a considerable energy lowering. The axial ligand makes the metal out-of-plane displacement even larger, and it also changes the redox properties of the lanthanide monoporphyrin. The ground-state configurations of YbP(2) and YbHP(2) were determined by considering several possible low-lying states. YbP(2) is confirmed to be a single-hole radical. The special redox properties of the bisporphyrin complexes can well be accounted for by the calculated ionization potentials and electron affinities. The TDDFT results provide a clear description of the UV-vis and near-IR absorption spectra of the various lanthanide porphyrins.
In the present mechanistic schemes of the ferroin-catalyzed oscillatory Belousov-Zhabotinsky (BZ) reaction the oxidation of the organic substrates (bromomalonic or malonic acid) by ferriin (the oxidized form of the catalyst) plays an important role. As the organic products of these reactions were not yet identified experimentally, they were studied here by an HPLC technique. It was found that the main organic oxidation product of bromomalonic acid is bromo-ethene-tricarboxylic acid (BrEETRA), the same compound that is formed when bromomalonic acid is oxidized by Ce4+ (another catalyst of the BZ reaction). Formation of BrEETRA is explained here by a new mechanism that is more realistic than the one suggested earlier. To find any oxidation product of malonic acid in the ferriin-malonic acid reaction was not successful, however. Neither ethane-tetracarboxylic acid (ETA) nor malonyl malonate (MAMA), the usual products of the Ce4+- malonic acid reaction, nor any other organic acid, not even CO2, was found as a product of the reaction. We propose that malonic acid is not oxidized in the ferriin-malonic acid reaction, and it plays only the role of a complex forming catalyst in a process where Fe3+ oxidizes mostly its phenantroline ligand.