0000000000350339
AUTHOR
Jianguo Shao
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…
Synthesis of an anthracenyl bridged porphyrin–corrole bismacrocycle. Physicochemical and electrochemical characterisation of the biscobalt μ-superoxo derivative
Abstract Dicobalt or heterobimetallic cofacial bisporphyrins are up till now amongst the very few molecular electrocatalysts able to promote the direct reduction of dioxygen to water via a four-electron process in acidic medium. Numerous studies have been devoted to elucidate the key steps of this catalytic reaction and an important result has revealed an unexpected high dioxygen affinity for a mixed valence Co(II)/Co(III) cofacial porphyrin, the key intermediate complex being a μ-superoxo derivative. At the same time, the great importance assumed by ‘Pacman’ porphyrins and the recent developments in corrole chemistry have provided the stimulation to synthesise porphyrin–corrole dyads which…
Alkyl- and aryl-substituted corroles. 4. Solvent effects on the electrochemical and spectral properties of cobalt corroles.
Solvent effects on the electrochemistry and spectroscopic properties of alkyl- and aryl-substituted corroles in nonaqueous media are reported. The oxidation and reduction of six compounds containing zero to seven phenyl or substituted phenyl groups on the macrocycle were studied in four different nonaqueous solvents (CH(2)Cl(2), PhCN, THF, and pyridine) containing 0.1 M tetra-n-butylammonium perchlorate. Dimers were formed upon oxidation of all corroles in CH(2)Cl(2), but this was not the case in the other three solvents, where either monomers or dimers were formed upon oxidation depending upon the solvent Gutmann donor number and the number or location of aryl substituents on the macrocycl…
Alkyl- and aryl-substituted corroles. 5. Synthesis, physicochemical properties, and X-ray structural characterization of copper biscorroles and porphyrin-corrole dyads.
The synthesis and characterization of cofacial copper biscorroles and porphyrin-corroles linked by a biphenylenyl or anthracenyl spacer are described. The investigated compounds are represented as (BCA)Cu(2) and (BCB)Cu(2) in the case of the biscorrole (BC) derivatives and (PCA)Cu(2) and (PCB)Cu(2) in the case of porphyrin (P)-corrole (C) dyads, where A and B represent the anthracenyl and biphenylenyl bridges, respectively. A related monomeric corrole (Me(4)Ph(5)Cor)Cu and monomeric porphyrin (Me(2)Et(6)PhP)Cu that comprise the two halves of the porphyrin-corrole dyads were also studied. Electron spin resonance (ESR), (1)H NMR, and magnetic measurements data demonstrate that the copper corr…
Electrochemical and spectroscopic characterization of cobalt and zinc diaza‐18‐crown‐6 porphyrins and of a zinc dioxocyclam porphyrin
The synthesis and electrochemical characterization of ‘crowned’ and ‘dioxocyclam’ metalloporphyrins containing Co(II) or Zn(II) metal ions is presented. Each complex is also characterized by mass spectrometry in addition to a variety of spectroscopic techniques (UV-vis, FTIR, ESR (in the case of Co(II)) and 1H and 13CNMR spectroscopy).
Electrochemistry and spectroelectrochemistry of heterobimetallic porphyrin-corrole dyads. Influence of the spacer, metal ion, and oxidation state on the pyridine binding ability.
Combined electrochemical and UV-visible spectroelectrochemical methods were utilized to elucidate the prevailing mechanisms for electroreduction of previously synthesized porphyrin-corrole dyads of the form (PCY)H2Co and (PCY)MClCoCl where M = Fe(III) or Mn(III), PC = porphyrin-corrole, and Y is a bridging group, either biphenylenyl (B), 9,9-dimethylxanthenyl (X), anthracenyl (A), or dibenzofuranyl (O). These studies were carried out in pyridine, conditions under which the cobalt(IV) corrole in (PCY)MClCoCl is immediately reduced to its Co(III) form, thus enabling direct comparisons with the free-base porphyrin dyad, (PCY)H2Co(III) under the same solution conditions. The compounds are all r…
Synthesis, physicochemical and electrochemical properties of metal–metal bonded ruthenium corrole homodimers
Abstract Two diruthenium(III,III) corrole dimers, [(Et 6 Me 2 Cor)Ru] 2 and [(Me 6 Et 2 Cor)Ru] 2 , where Et 6 Me 2 Cor and Me 6 Et 2 Cor are the 2,3,8,12,17,18-hexaethyl-7,13-dimethylcorrole and 8,12-diethyl-2,3,7,13,17,18-hexamethylcorrole trianions, respectively, were synthesized and characterized as to their spectroscopic and electrochemical properties. They exhibit up to three oxidations and two reductions by cyclic voltammetry in CH 2 Cl 2 or pyridine containing 0.1 M TBAP, almost all of which are electrochemically reversible on the voltammetric and/or thin-layer spectroelectrochemical timescale. The two reductions and the first two oxidations involve one-electron transfer processes w…
Solvent, anion and structural effects on the redox potentials and UV-visible spectral properties of mononuclear manganese corroles
A series of manganese(III) corroles were investigated as to their electrochemistry and spectroelectrochemistry in nonaqueous solvents. Up to three oxidations and one reduction were obtained for each complex depending on the solvents. The main compound discussed in this paper is the meso-substituted manganese corrole, (Mes 2PhCor)Mn, and the main points are how changes in axially coordinated anion and solvent will affect the redox potentials and UV-vis spectra of each electrogenerated species in oxidation states of Mn(III), Mn(IV), or Mn(II). The anions OAc (-), Cl (-), CN (-), and SCN (-) were found to form five-coordinate complexes with the neutral Mn(III) corrole while two OH (-) or F (-)…
Alkyl and aryl substituted corroles. 3. Reactions of cofacial cobalt biscorroles and porphyrin-corroles with pyridine and carbon monoxide.
The synthesis and characterization of three new cofacial biscorroles and three new linked Co(II) porphyrins and Co(III) corroles with the same face to face orientation are described. The biscorroles are represented as (BCS)Co(2), (BCO)Co(2), (BCX)Co(2) while the porphyrin-corrole dyads are represented as (PCA)Co(2), (PCB)Co(2), (PCO)Co(2) where BC represents the Co(III) cofacial biscorroles and PC represents the porphyrin-corrole complexes which are linked to each other by a dibenzothiophene (S), dibenzofuran (O), or 9,9-dimethylxanthene (X) bridge in the case of the corroles and an anthracene (A), biphenylene (B), or dibenzofuran (O) bridge in the case of the mixed macrocycle derivatives. …
Heterobimetallic complexes of cobalt(IV) porphyrin-corrole dyads. Synthesis, physicochemical properties, and X-ray structural characterization.
The synthesis of a novel family of heterobinuclear cofacial biphenylene (B), anthracene (A), 9,9-dimethylxanthene (X), or dibenzofuran (O) bridged porphyrin-corrole complexes, (PCY)MClCoCl, is reported, M being either an iron(III) or manganese(III) ion. Each complex was characterized by electrochemistry, mass spectrometry, UV-vis, IR, and electron spin resonance spectroscopy. Unlike previously examined biscobalt porphyrin-corrole dyads, the cobalt ion of the corrole moiety is present in a high-valence +4 oxidation state, as proven by electrochemistry, spectroelectrochemistry, and an X-ray diffraction study of (PCB)FeClCoCl, which shows the presence of a bound Cl- anion on the cobalt corrole…
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 …
Electrochemistry, spectroelectrochemistry, chloride binding, and O2 catalytic reactions of free-base porphyrin-cobalt corrole dyads.
Three face-to-face linked porphyrin-corrole dyads were investigated as to their electrochemistry, spectroelectrochemistry, and chloride-binding properties in dichloromethane or benzonitrile. The same three compounds were also investigated as to their ability to catalyze the electroreduction of dioxygen in aqueous 1 M HClO4 or HCl when adsorbed on a graphite electrode. The characterized compounds are represented as (PCY)H2Co, where P = a porphyrin dianion; C = a corrole trianion; and Y = a biphenylenyl, 9,9-dimethylxanthenyl, or anthracenyl spacer, which links the two macrocycles in a face-to-face arrangement. An axial binding of one or two Cl- ligands to the cobalt center of the corrole is …
CCDC 168247: Experimental Crystal Structure Determination
Related Article: R.Guilard, C.P.Gros, F.Bolze, F.Jerome, Zhongping Ou, Jianguo Shao, J.Fischer, R.Weiss, K.M.Kadish|2001|Inorg.Chem.|40|4845|doi:10.1021/ic010177+
CCDC 257240: Experimental Crystal Structure Determination
Related Article: R.Guilard, C.P.Gros, J.-M.Barbe, E.Espinosa, F.Jerome, A.Tabard, J.-M.Latour, Jianguo Shao, Zhongping Ou, K.M.Kadish|2004|Inorg.Chem.|43|7441|doi:10.1021/ic049651c
CCDC 257242: Experimental Crystal Structure Determination
Related Article: R.Guilard, C.P.Gros, J.-M.Barbe, E.Espinosa, F.Jerome, A.Tabard, J.-M.Latour, Jianguo Shao, Zhongping Ou, K.M.Kadish|2004|Inorg.Chem.|43|7441|doi:10.1021/ic049651c
CCDC 168248: Experimental Crystal Structure Determination
Related Article: R.Guilard, F.Jerome, J.-M.Barbe, C.P.Gros, Zhongping Ou, Jianguo Shao, J.Fischer, R.Weiss, K.M.Kadish|2001|Inorg.Chem.|40|4856|doi:10.1021/ic0101782
CCDC 275363: Experimental Crystal Structure Determination
Related Article: R.Guilard, F.Burdet, J.-M.Barbe, C.P.Gros, E.Espinosa, Jianguo Shao, Zhongping Ou, Riqiang Zhan, K.M.Kadish|2005|Inorg.Chem.|44|3972|doi:10.1021/ic0501622
CCDC 257241: Experimental Crystal Structure Determination
Related Article: R.Guilard, C.P.Gros, J.-M.Barbe, E.Espinosa, F.Jerome, A.Tabard, J.-M.Latour, Jianguo Shao, Zhongping Ou, K.M.Kadish|2004|Inorg.Chem.|43|7441|doi:10.1021/ic049651c