388076-03-7Relevant articles and documents
Spectroelectrochemical characterization of meso triaryl-substituted Mn(IV), Mn(III) and Mn(II) corroles. Effect of solvent and oxidation state on UV-visible spectra and redox potentials in nonaqueous media
Gao, Bingbing,Ou, Zhongping,Chen, Xueyan,Huang, Shi,Li, Bihong,Fang, Yuanyuan,Kadish, Karl M.
, p. 131 - 144 (2014)
Two series of substituted manganese triarylcorroles were synthesized and characterized as to their electrochemical and spectroelectrochemical properties in CH2Cl2, CH3CN and pyridine. The investigated compounds are represented as (YPh)3CorMnIII and (YPh)3CorMnIVCl, where Cor is a trianion of the corrole and Y is a Cl, F, H or CH3 para-substituent on the three phenyl rings of the macrocycle. Each neutral Mn(III) corrole exists as a four-coordinate complex in CH2Cl2 and CH3CN and as a five-coordinate species in pyridine. (YPh)3CorMnIII undergoes two oxidations to stepwise generate a Mn(IV) corrole and a Mn(IV) μ-cation radical. It also undergoes one reduction to generate a Mn(II) corrole in CH2Cl2 or CH3CN. In contrast, the reduction of (YPh)3CorMnIII leads to a Mn(III) corrole μ-anion radical in pyridine. One oxidation is observed for (YPh)3CorMnIVCl in CH2Cl2 and CH3CN to generate a Mn(IV) corrole μ-cation radical while Mn(III) and Mn(II) corroles are stepwise formed after reduction of the same compound. The second reduction of (YPh)3CorMnIVCl in pyridine gives a Mn(III) μ-anion radical as opposed to a Mn(II) corrole with an unreduced μ-ring system. The neutral, reduced and oxidized forms of each corrole were characterized by electrochemistry and UV-visible spectroelectrochemistry and comparisons are made between the UV-visible spectra and redox potentials of the compounds in different central metal oxidation states. An overall reduction/oxidation mechanism in the three solvents is proposed.
Synthetic and mechanistic investigations on manganese corrole-catalyzed oxidation of sulfides with iodobenzene diacetate
Ranburger, Davis,Willis, Ben,Kash, Benjamin,Jeddi, Haleh,Alcantar, Christian,Zhang, Rui
, p. 41 - 49 (2018/12/11)
Manganese corrole complexes catalyze the efficient oxidation of organic sulfides to sulfoxides with iodobenzene diacetate [PhI(OAc)2] as a mild oxygen source in the presence of small amounts of water. Various substituted thioanisoles can be eff
Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence
Ganguly, Sumit,McCormick, Laura J.,Conradie, Jeanet,Gagnon, Kevin J.,Sarangi, Ritimukta,Ghosh, Abhik
, p. 9656 - 9669 (2018/08/28)
Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = 3/2 manganese corrole derivatives at the formal MnIV oxidation state. The Soret maxima of Mn[TpXPC]Cl (TpXPC = meso-tris(p-X-phenyl)corrole, where X = CF3, H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[TpXPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X. These observations suggested a noninnocent corrole·2--like ligand for the MnCl complexes and an innocent corrole3- ligand for the MnPh complexes. Single-crystal X-ray structures of three Mn[TpXPC]Cl complexes revealed skeletal bond-length alternations indicative of a noninnocent corrole, while no such alternation was observed for Mn[TpOMePC]Ph. B3LYP density functional theory (DFT) calculations on Mn[TPC]Cl yielded strong spatial separation of the α and β spin densities, consistent with an antiferromagnetically coupled MnIII-corrole·2- description. By comparison, relatively little spatial separation of the α and β spin densities was found for Mn[TPC]Ph, consistent with an essentially MnIV-corrole3- description. X-ray absorption of near-edge spectroscopy (XANES) revealed a moderate blue shift of 0.6 eV for the Mn K-pre-edge of Mn[TpCF3PC]Ph and a striking enhancement of the pre-edge intensity, relative to Mn[TpCF3PC]Cl, consistent with a more oxidized, i.e., MnIV, center in Mn[TpCF3PC]Ph. Time-dependent DFT calculations indicated that the enhanced intensity of the Mn K-pre-edge of Mn[TpCF3PC]Ph results from the extra 3dz2 hole, which mixes strongly with the Mn 4pz orbital. Combined with similar results on Fe[TPC]Cl and Fe[TPC]Ph, the present study underscores the considerable potential of metal K-edge XANES in probing ligand noninnocence in first-row transition-metal corroles. Cyclic voltammetry measurements revealed highly negative first reduction potentials for the Mn[TpXPC]Ph series (～-0.95 V) as well as large electrochemical HOMO-LUMO gaps of ～1.7 V. The first reductions, however, are irreversible, suggesting cleavage of the Mn-Ph bond.
