0000000000350337
AUTHOR
Jean Fischer
Alkyl and Aryl Substituted Corroles. 2. Synthesis and Characterization of Linked “Face-to-Face” Biscorroles. X-ray Structure of (BCA)Co2(py)3, Where BCA Represents a Biscorrole with an Anthracenyl Bridge
The synthesis, spectroscopic properties, and electrochemistry of (BCA)Co(2) and (BCB)Co(2) are described where BCA and BCB represent biscorroles linked by an anthracenyl (A) or a biphenylenyl (B) bridge. The pyridine and CO binding properties of (BCA)Co(2) and (BCB)Co(2) are also presented, and one of the compounds in its pyridine-ligated form, (BCA)Co(2)(py)(3), is structurally characterized. The data on the biscorroles are compared on one hand to the monocorrole having the same substitution pattern and on the other hand to bisporphyrins having two Co(II) ions and the same anthracenyl or biphenylenyl linkers in order to better understand the interaction which occurs between the two corrole…
Structure and mixed spin state of the chloroiron(III) complex of 2,3,7,8,12,13,17,18-octaphenyl-5,10,15,20-tetraphenylporphyrin, Fe(dpp)Cl
Abstract The chloroiron(III) complex Fe(dpp)Cl (1) of the peripherally crowded 2,3,7,8,12,13,17,18-octaphenyl-5,10,15,20-tetraphenylporphyrin or dodecaphenylporphyrin (dpp), has been synthesized and characterized by X-ray crystallography, normal-coordinate structural decomposition analysis (NSD), EPR and Mossbauer spectroscopy and magnetic susceptibility measurements. The dpp ligand present in the crystal structure of this molecule is predominantly saddle-shaped. It is also ruffled and slightly domed according to an analysis of the out-of-plane distortions performed by using NSD. This saddle deformation is significantly smaller than those observed in the chloroiron(III) complexes of the β-p…
Alkyl and Aryl Substituted Corroles. 1. Synthesis and Characterization of Free Base and Cobalt Containing Derivatives. X-ray Structure of (Me4Ph5Cor)Co(py)2
The synthesis, spectroscopic properties, and electrochemistry of six different alkyl- and aryl-substituted Co(III) corroles are presented. The investigated compounds contain methyl, ethyl, phenyl, or substituted phenyl groups at the eight β-positions of the corrole macrocycle and four derivatives also contain a phenyl group at the 10-meso position of the macrocycle. Each cobalt corrole undergoes four reversible oxidations in CH2Cl2 containing 0.1 M tetra-n-butylammonium perchlorate and exists as a dimer in its singly and doubly oxidized forms. The difference in potential between the first two oxidations is associated with the degree of interaction between the two corrole units of the dimer …
The 5/2,3/2 Spin Admixture in the Chloroiron(III) Derivative of the Sterically Crowded 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetraphenylporphyrin
Despite similar ring deformations in solution and in the solid state, the chloroiron(III) derivative of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin ([FeCl(oetpp)], shown schematically) prepared in this study exhibits only a very weak quantum-mechanical admixture of spin S=3/2 (only 4-10 %) with spin S=5/2. In contrast, for the variety of [FeCl(oetpp)] studied earlier by other researchers a 40 % contribution of the S=3/2 state was found.
Mössbauer investigations of the hexachlorantimonate salt of the phenyliron 2,3,7,8,l2,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrinate, [Fe(oetpp)Ph]SbCl6 and X-ray structure of the phenyliron(III) precursor Fe(III)(oetpp)Ph
Abstract The phenyliron derivative, [Fe(oetpp)C6H5)]SbCl6 (2) generated in dichloromethane by oxidation of the phenyliron(III) complex, Fe(III) (oetpp)C6H5 (1) of the 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin with 1 equiv. of phenoxathiinylium hexachloroantimonate, [C12H8OS]SbCl6, was studied by Mossbauer spectroscopy. This compound exhibits an isomer shift δ of 0.13 mm s−1 and a quadrupole splitting ΔEQ of 3.23 mm s−1. The measured magnetic hyperfine pattern obtained in the temperature range 4.2–40 K in a field of 3.5 and 7 T, applied perpendicular to the γ-beam, has been consistently analyzed in the spin Hamiltonian approximation assuming an iron(IV) S=1 electronic con…