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 macrocycle. The half-wave potentials were analyzed as a function of the number of aryl substituents on the macrocycle as well as the concentration of added pyridine to PhCN solutions of the compound, and these data were combined with data from the spectroelectrochemistry experiments to determine the stoichiometry of the species actually in solution after the first oxidation or first reduction of each compound. The results of these experiments indicate that reduction of the bispyridine adduct (Cor)Co(III)(py)(2) proceeds via the monopyridine complex (Cor)Co(III)(py) to give in each case the unligated cobalt(II) corrole [(Cor)Co(II)](-). In contrast, pyridine remains coordinated after electrooxidation, and the final product was characterized as [(Cor)Co(III)(py)(2)](+).     

Protonated free-base corroles: acidity, electrochemistry, and spectroelectrochemistry of [(Cor)H4]+, [(Cor)H5]2+, and [(Cor)H6]3+

Protonated meso-substituted free-base macrocycles of the form [(Cor)H4]+, [(Cor)H5]2+, and [(Cor)H6]3+ where Cor is the trianion of a given corrole, were chemically generated from neutral (Cor)H3 in benzonitrile by addition of trifluoroacetic acid (TFA) and characterized as to their relative acidity, electrochemistry, and spectroelectrochemistry. Three types of protonated free-base corroles with different electron-donating or electron-withdrawing substituents at the meso positions of the macrocycle were investigated. One is protonated exclusively at the central nitrogens of the corrole forming [(Cor)H4]+ from (Cor)H3, while the second and third types of corroles undergo protonation at one or two meso pyridyl substituents prior to protonation of the central nitrogens and give as the final products [(Cor)H5]2+ and [(Cor)H6]3+, respectively. Altogether the relative deprotonation constants (pKa) for 10 different corroles were determined in benzonitrile and analyzed with respect to the molecular structure and/or type of substituents on the three meso positions of the macrocycle. Mechanisms for oxidation and reduction of the protonated corroles are proposed in light of the electrochemical and spectroelectrochemical data.     

Electrochemistry and spectroelectrochemistry of meso-substituted free-base corroles in nonaqueous media: reactions of (Cor)H3, [(Cor)H4]+, and [(Cor)H2]-

Eleven free-base corroles with different electron-donating or electron-withdrawing meso substituents were characterized as to their electrochemistry and UV-visible spectroscopy in benzonitrile (PhCN) or pyridine containing tetra-n-butylammonium perchlorate (0.1 M). Six forms of the compounds with different numbers of protons and/or oxidation states were spectroscopically identified and are represented as (Cor)H3, (.Cor)H2, [(Cor)H2]-, [(.Cor)H2]2-, [(Cor)H4]+, and [(.Cor)H4]2+, where Cor is a trianionic corrole macrocycle. The electrochemistry and UV-visible properties are a function of corrole basicity, solvent basicity, and types or sizes of the meso substituents, and the compounds could be subdivided into one of two different groups, one of which comprises sterically hindered corroles and another that does not. The electroactive species in PhCN is (Cor)H3, whereas in pyridine, one inner proton dissociates, generating a mixture of (Cor)H3, [(Cor)H2]-, and pyH+. The addition of one electron to [(Cor)H2]- reversibly gives the [(.Cor)H2]2- pi-anion radical, whereas a reversible oxidation of the same species gives the neutral radical (.Cor)H2. The first one-electron reduction of (Cor)H3 occurs at the macrocycle in PhCN, but the initial product rapidly converts to [(Cor)H2]-, which undergoes additional reversible redox reactions at the conjugated pi-ring system. The first oxidation of (Cor)H3 in PhCN leads to a mixture of (.Cor)H2 and [(Cor)H4]+, both of which could be further oxidized or reduced. The UV-visible spectra of [(Cor)H4]+ were measured in PhCN after titrations with trifluoroacetic acid, after which selected samples were examined as to their electrochemistry. The HOMO-LUMO gaps of [(Cor)H2]-, (Cor)H3, and [(Cor)H4]+ were also determined.     

Photophysical properties of a series of free-base corroles

Four free-base corroles with electron-donating or electron-withdrawing groups on the para or 2 through 6-positons of the meso phenyl rings were prepared via either Paolesse or Gross conditions and investigated for their absorption and emission properties. The triaryl corroles 5,10,15-triphenylcorrole, 5,10,15-tris(pentafluorophenyl)corrole, 5,10,15-tris(p-nitrophenyl)corrole, and 5,10,15-tris(p-methoxyphenyl)corrole were examined. Absorption, steady-state, and time-resolved fluorescence measurements were performed on all compounds in both nonpolar (dichloromethane) and polar (dimethylacetamide) solvents. The experimental evidence points to hydrogen bonding with an internal N-H group as the most likely factor in the solvent-dependent photophysical behavior of these corroles, that is also highly dependent upon substitution.     

Alkyl and aryl substituted corroles. 1. Synthesis and characterization of free base and cobalt containing derivatives. x-ray structure of (Me(4)Ph(5)Cor)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 beta-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 CH(2)Cl(2) 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 and ranges from an upper value of 0.62 V, in the case of (Me(6)Et(2)Cor)Co, to a lower value of about 0.17 V, in the case of four compounds which have a phenyl group located at the 10-meso position of the macrocycle. These Co(III) corroles strongly coordinate two pyridine molecules or one carbon monoxide molecule in CH(2)Cl(2) media, and ligand binding constants were evaluated using spectroscopic and electrochemical methods. The structure of (Me(4)Ph(5)Cor)Co(py)(2) was also determined by X-ray diffraction. Crystal data: (Me(4)Ph(5)Cor)Co(py)(2).3CH(2)Cl(2).H(2)O, orthorhombic, a = 19.5690(4) A, b = 17.1070(6) A, c = 15.9160(6) A, V = 5328.2(5) A(3), space group Pna2(1), Z = 2, 35 460 observations, R(F) = 0.069.     

新型氯代苯基咔咯的合成及电化学和光谱性质

通过吡咯和具有相应取代基的苯甲醛在甲醇和水的混合溶剂中生成胆色烷, 然后用四氯苯醌氧化胆色烷, 合成了2种新型的咔咯化合物: 三(4-氯苯基)咔咯[(ClPh)₃CorH₃]和三(2,4-二氯苯基)咔咯[(Cl₂Ph)₃CorH₃]. 采用紫外-可见、荧光、¹H NMR、MS和IR等光谱技术对化合物进行了表征. 研究了化合物在二氯甲烷和二甲基甲酰胺中的电化学及光谱电化学性质. 讨论了溶剂和取代基对紫外-可见光谱以及氧化还原电位和电子转移过程的影响. 提出了化合物在2种不同溶剂中的氧化还原反应机理.     

Electronic structures of Group 9 metallocorroles with axial ammines

The electronic structures of metallocorroles (tpfc)M(NH(3))(2) and (tfc)M(NH(3))(2) (tpfc is the trianion of 5,10,15-(tris)pentafluorophenylcorrole, tfc is the trianion of 5,10,15-trifluorocorrole, and M = Co, Rh, Ir) have been computed using first principles quantum mechanics [B3LYP flavor of Density Functional Theory (DFT) with Poisson-Boltzmann continuum solvation]. The geometry was optimized for both the neutral systems (formal M(III) oxidation state) and the one-electron oxidized systems (formally M(IV)). As expected, the M(III) systems have a closed shell d(6) configuration; for all three metals, the one-electron oxidation was calculated to occur from a ligand-based orbital (highest occupied molecular orbital (HOMO) of B(1) symmetry). The ground state of the formal M(IV) system has M(III)-Cπ character, indicating that the metal remains d(6), with the hole in the corrole π system. As a result the calculated M(IV/III) reduction potentials are quite similar (0.64, 0.67, and 0.56 V vs SCE for M = Ir, Rh and Co, respectively), whereas the differences would have been large for purely metal-based oxidations. Vertically excited states with substantial metal character are well separated from the ground state in one-electron-oxidized cobalt (0.27 eV) and rhodium (0.24 eV) corroles, but become closer in energy in the iridium (0.15 eV) analogues. The exact splittings depend on the chosen functional and basis set combination and vary by ~0.1 eV.     

两种甲氧基苯基咔咯铜配合物的合成及光谱性质

合成了两个中位苯基上具有甲氧基取代基的铜咔咯配合物(Tp-OCH3PC)Cu和(To,p-(OCH3)2PC)Cu,通过紫外-可见、红外光谱、元素分析、核磁共振及质谱对它们进行了表征。研究了配合物在非水溶剂中的电子顺磁共振、电化学和光谱电化学性质,结果表明无论在固体状态还是在非水溶剂中,配合物的中心金属离子均为三价铜Cu(Ⅲ),在给定的溶剂中Cu(Ⅲ)可以发生可逆的还原反应生成Cu(Ⅱ),也可以被可逆氧化为Cu(Ⅲ)的阳离子自由基。探讨了甲氧基取代基以及溶剂对配合物的紫外-可见光谱和氧化还原电位的影响。     

Synthesis and functionalization of meso-aryl-substituted corroles.

The Rothemund condensation reaction of pyrrole and aldehydes is an extensively used route to meso-tetraarylporphyrins, but simple modifications of the reaction conditions allow the formation of different macrocycles other than the expected porphyrin. In the presence of an excess of pyrrole, this modified Rothemund approach leads to the synthesis of meso-triary-substituted corroles. This methodology allows the preparation of a wide range of substituted corroles starting from commercially available products. Higher yields have been obtained in the case of benzaldehydes bearing electron-withdrawing substituents, while the reaction fails in the presence of 2,6-disubstituted benzaldehydes. Although if not isolated, some experimental evidences indicate that the linear 5,10,15-triphenylbilane 4 is the precursor of the final corrole ring. Reaction of 5,10,15-triphenylcorrole 2 with an excess of NBS leads to the complete bromination of the macrocycle. Spectroscopic characterization seems to indicate the formation of the porphodimethene-like structure 5, where the macrocyclic aromatic conjugation is interrupted at the 10 position. Metalation of this compound with cobalt acetate and PPh3 affords the corresponding complex. The X-ray crystal structure of triphenylphosphine [2,3,7,8,12,13,17,18-octabromo-5,10,15-tris(4-nitrophenyl)corrolato]- cobalt(III) 8 confirms the ability of corrole ring to retain an almost planar conformation when fully substituted at the peripheral position.     

Reductive demetalation of manganese corroles： The substituent effect

The reductive demetalation of manganese corroles was investigated in CH2Cl2/HCl （aqueous） solvent by using SnCl2 as reducing agent. It was found that the demetalation yields depend on the substituents of corrole macrocycle significantly. Electron- rich manganese corrole undergoes reductive demetalation more easily than electron-deficient ones. The isolated reductive demetalation yield of manganese 5,10,15-tris（phenyl）corrole in present system is moderate （46%）. As for electron-deficient Mn（Ⅲ） 5,10,15-tris（pentafluorophenyl）corrole, the acid-induced demetalation in HOAc-HESO4 （V/V = 3：1） is preferable with an isolated yield of 67%.     

Cobalt Triarylcorroles with Sterically Hindered Haloginated Phenyl Rings:Synthesis,Crystal Structure and Catalytic Activity for Electroreduction of Dioxygen

Three new cobalt triarylcorroles with sterically hindered haloginated phenyl rings were synthesized and characterized by UV-vis, ~1H NMR spectroscopy, mass spectrometry and electrochemistry. The compounds are represented as(Ar)3Cor Co(PPh3), where Cor is a trianion of the corrole macrocycle and Ar is a 2-Cl Ph(1), 2,6-diC l Ph(2) or 2,6-diF Ph(3) group on each of the three meso-positions. The structures of 1 and 3 were characterized in the solid state by single-crystal X-ray analysis. Rotating-disk electrode was utilized to examine the electrocatalytic activity of the corroles for reduction of O_2 in 1.0 MHClO_4. Effect of the sterically hindered meso-substituents on UV-vis spectra and redox potentials as well as the electrocatalytic activity for reduction of dioxygen was discussed.     

Xanthene-modified and hangman iron corroles

Iron corroles modified with a xanthene scaffold are delivered from easily available starting materials in abbreviated reaction times. These new iron corroles have been spectroscopically examined with particular emphasis on defining the oxidation state of the metal center. Investigation of their electronic structure using (57)Fe Mo?ssbauer spectroscopy in conjunction with density functional theory (DFT) calculations reveals the non-innocence of the corrole ligand. Although these iron corroles contain a formal Fe(IV) center, the deprotonated corrole macrocycle ligand is one electron oxidized. The electronic ground state of these complexes is best described as an intermediate spin S = 3/2 Fe(III) site strongly antiferromagnetically coupled to the S = 1/2 of the monoradical dianion corrole [Fe(III)Cl-corrole(+?)]. We show here that iron corroles as well as xanthene-modified and hangman xanthene iron corroles are redox active and catalyze the disproportionation of hydrogen peroxide via the catalase reaction, and that this activity scales with the oxidation potential. The meso position of corrole macrocycle is susceptible toward nucleophilic attack during catalase turnover. The reactivity of peroxide within the hangman cleft reported here adds to the emerging theme that corroles are good at catalyzing two-electron activation of the oxygen-oxygen bond in a variety of substrates.     

Cobalt(III) corroles as electrocatalysts for the reduction of dioxygen: reactivity of a monocorrole, biscorroles, and porphyrin-corrole dyads

Three series of cobalt(III) corroles were tested as catalysts for the electroreduction of dioxygen to water. One was a simple monocorrole represented as (Me(4)Ph(5)Cor)Co, one a face-to-face biscorrole linked by an anthracene (A), biphenylene (B), 9,9-dimethylxanthene (X), dibenzofuran (O) or dibenzothiophene (S) bridge, (BCY)Co(2) (with Y = A, B, X, O or S), and one a face-to-face bismacrocyclic complex, (PCY)Co(2), containing a Co(II) porphyrin and a Co(III) corrole also linked by one of the above rigid spacers (Y = A, B, X, or O). Cyclic voltammetry and rotating ring-disk electrode voltammetry were both used to examine the catalytic activity of the cobalt complexes in acid media. The mixed valent Co(II)/Co(III) complexes, (PCY)Co(2), and the biscorrole complexes, (BCY)Co(2), which contain two Co(III) ions in their air-stable forms, all provide a direct four-electron pathway for the reduction of O(2) to H(2)O in aqueous acidic electrolyte when adsorbed on a graphite electrode, with the most efficient process being observed in the case of the complexes having an anthracene spacer. A relatively small amount of hydrogen peroxide was detected at the ring electrode in the vicinity of E(1/2) which was located at 0.47 V vs SCE for (PCA)Co(2) and 0.39 V vs SCE for (BCA)Co(2). The cobalt(III) monocorrole (Me(4)Ph(5)Cor)Co also catalyzes the electroreduction of dioxygen at E(1/2) = 0.38 V with the final products being an approximate 50% mixture of H(2)O(2) and H(2)O.     

Synthesis of corroles bearing up to three different meso substituents

[reaction: see text] We have developed a new method that affords regioisomerically pure corroles possessing up to three different substituents at the meso positions. The corrole formation reaction involves the acid-catalyzed condensation of a dipyrromethane-dicarbinol with pyrrole followed by oxidation with DDQ. ABC-Type corroles were synthesized for the first time according to this procedure.     

Molecular Oxygen Reduction Electrocatalyzed by meso-Substituted Cobalt Corroles Coated on Edge-Plane Pyrolytic Graphite Electrodes in Acidic Media

Five meso-substituted cobalt(III) corroles were examined as to their catalytic activity for the electoreduction of O(2) when coated on an edge-plane pyrolytic graphite electrode in 1.0 M HClO(4). The investigated compounds are represented as (TpRPCor)Co(PPh(3)), where TpRPCor is the trianion of a para-substituted triphenylcorrole and R = OMe, Me, H, F, or Cl. Three electrochemical techniques, cyclic voltammetry, linear sweep voltammetry with a rotating disk electrode (RDE), and voltammetry at a rotating ring disk electrode (RRDE), were utilized to evaluate the catalytic activity of the corroles in the reduction of O(2). Cobalt corroles containing electron-withdrawing substituents were shown to be better catalysts than those having electron-donating groups on the three meso-phenyl rings of the triarylcorroles.     

Electrochemical and Spectral Characterization of Iron Corroles in High and Low Oxidation States: First Structural Characterization of an Iron(IV) Tetrapyrrole pi Cation Radical

The electrochemistry and spectroscopic properties of three iron corroles were examined in benzonitrile, dichloromethane, and pyridine containing 0.1 M tetra-n-butylammonium perchlorate or tetra-n-ethylammonium hexafluorophosphate as supporting electrolyte. The investigated compounds are represented as (OEC)Fe(IV)(C(6)H(5)), (OEC)Fe(IV)Cl, and (OEC)Fe(III)(py), where OEC is the trianion of 2,3,7,8,12,13,17,18-octaethylcorrole. Each iron(IV) corrole undergoes two one-electron reductions and two or three one-electron oxidations depending upon the solvent. Under the same solution conditions, the iron(III) corrole undergoes a single one-electron reduction and one or two one-electron oxidations. Each singly oxidized and singly reduced product was characterized by UV-vis and/or EPR spectroscopy. The data indicate a conversion of (OEC)Fe(IV)(C(6)H(5)) and (OEC)Fe(IV)Cl to their iron(III) forms upon a one-electron reduction and to iron(IV) corrole pi cation radicals upon a one-electron oxidation. The metal center in [(OEC)Fe(III)(C(6)H(5))](-) is low spin (S = (1)/(2)) as compared to electrogenerated [(OEC)Fe(III)Cl](-), which contains an intermediate-spin (S = (3)/(2)) iron(III). (OEC)Fe(III)(py) also contains an intermediate-spin-state iron(III) and, unlike previously characterized (OEC)Fe(III)(NO), is converted to an iron(IV) corrole upon oxidation rather than to an iron(III) pi cation radical. Singly oxidized [(OEC)Fe(IV)(C(6)H(5))](*)(+) is the first iron(IV) tetrapyrrole pi cation radical to be isolated and was structurally characterized as a perchlorate salt. It crystallizes in the triclinic space group P&onemacr; with a = 10.783(3) ?, b = 13.826(3) ?, c = 14.151(3) ?, alpha = 78.95(2) degrees, beta = 89.59(2) degrees, and gamma = 72.98(2) degrees at 293 K with Z = 2. Refinement of 8400 reflections and 670 parameters against F(o)(2) yields R1 = 0.0864 and wR2 = 0.2293. The complex contains a five-coordinated iron with average Fe-N bond lengths of 1.871(3) ?. The formulation of the electron distribution in this compound was confirmed by M?ssbauer, X-ray crystallographic, and magnetic susceptibility data as well as by EPR spectroscopy, which gives evidence for strong antiferromagnetic coupling between the iron(IV) center and the singly oxidized corrole macrocycle.