246231-46-9

Upstream product

• 6147-53-1 cobalt(II) diacetate tetrahydrate 
• 603-35-0 triphenylphosphine 
• 305831-41-8 2-[phenyl(1H-pyrrol-2-yl)methyl]-5-(phenyl{5-[phenyl(1H-pyrrol-2-yl)methyl]-1H-pyrrol-2-yl}methyl)-1H-pyrrole 
• 71-48-7 cobalt(II) acetate 

Relevant academic research and scientific papers

5,10,15-Triphenylcorrole: A product from a modified Rothemund reaction

One-pot synthesis of 5,10,15-triphenylcorrole has been achieved by reaction of benzaldehyde with an excess of pyrrole; the triphenylphosphinocobalt complex of 5,10,15-triphenylcorrole has been structurally characterized using X-ray crystallography.

Electrocatalytic activity of cobalt tris(4-nitrophenyl)corrole for hydrogen evolution from water

Catalytic activities for hydrogen (H2) evolution of cobalt 5,10,15-tris(phenyl)corrole (1) and 5,10,15-tris(4-nitrophenyl)corrole (2) (in homogeneous system was examined from acetic acid and water. In phosphate buffer solution (pH 7.0), the hyd

Application of [Co(Corrole)]– Complexes in Ring-Closing C–H Amination of Aliphatic Azides via Nitrene Radical Intermediates

The synthesis, characterisation and application of anionic [CoII(Cor)]– (Cor = corrole) metalloradicals in the ring-closing C–H amination of an aliphatic azide in the presence of Boc2O (Boc = tert-butyloxycarbonyl) to give the corresponding Boc-protected N-heterocyclic product tert-butyl 2-phenylpyrrolidine-1-carboxylate are reported. This is the first example of the use of metalloradical cobalt(II) corrole complexes in nitrene-transfer reactions. On the basis of DFT calculations, the reaction is proposed to proceed via discrete open-shell nitrene radical intermediates bearing most of their spin density at the nitrene nitrogen atom. The [CoII(Cor)]– complexes are substantially faster catalysts than the corresponding neutral [CoII(porphyrin)] complexes when applied in the same ring-closing C–H amination reaction under identical reaction conditions. Increasing the electron density at cobalt(II) therefore has a positive influence on the reaction rate.

Cobalt- and Rhodium-Corrole-Triphenylphosphine Complexes Revisited: The Question of a Noninnocent Corrole

A reinvestigation of cobalt-corrole-triphenylphosphine complexes has yielded an unexpectedly subtle picture of their electronic structures. UV-vis absorption spectroscopy, skeletal bond length alternations observed in X-ray structures, and broken-symmetry DFT (B3LYP) calculations suggest partial CoII-corrole?2- character for these complexes. The same probes applied to the analogous rhodium corroles evince no evidence of a noninnocent corrole. X-ray absorption spectroscopic studies showed that the Co K rising edge of Co[TPC](PPh3) (TPC = triphenylcorrole) is red-shifted by ～1.8 eV relative to the bona fide Co(III) complexes Co[TPC](py)2 and Co[TPP](py)Cl (TPP = tetraphenylporphyrin, py = pyridine), consistent with a partial CoII-corrole?2- description for Co[TPC](PPh3). Electrochemical measurements have shown that both the Co and Rh complexes undergo two reversible oxidations and one to two irreversible reductions. In particular, the first reduction of the Rh corroles occurs at significantly more negative potentials than that of the Co corroles, reflecting significantly higher stability of the Rh(III) state relative to Co(III). Together, the results presented herein suggest that cobalt-corrole-triphenylphosphine complexes are significantly noninnocent with moderate CoII-corrole?2- character, underscoring - yet again - the ubiquity of ligand noninnocence among first-row transition metal corroles.

Cobalt triarylcorroles containing one, two or three nitro groups. Effect of NO2 substitution on electrochemical properties and catalytic activity for reduction of molecular oxygen in acid media

Cobalt(III) triarylcorroles containing 0-3 nitro groups on the para-position of the three meso-phenyl rings of the macrocycle were synthesized and characterized by electrochemistry, mass spectrometry, (UV-vis) and 1H NMR spectroscopy. The examined compounds are represented as (NO2Ph)nPh3 - nCorCo(PPh3), where n varies from 0 to 3 and Cor represents the core of the corrole. Each compound can undergo two metal-centered one-electron reductions leading to formation of Co(II) and Co(I) derivatives in CH2Cl2 or pyridine containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). A stepwise two electron reduction of each NO2Ph group of the compound is also observed. The first is reversible and occurs in a single overlapping step at the same potential which involves an overall one-, two- or three-electron transfer process for compounds 2-4, respectively. This indicates the lack of an interaction between these redox active sites on the corroles. The second reduction of the NO2Ph groups is irreversible and located at a potential which overlaps the Co(II)/Co(I) process of the compounds. Thin-layer UV-visible spectroelectrochemical measurements in CH2Cl2, 0.1 M TBAP demonstrate the occurrence of an equilibrium between a Co(III) π-anion radical and a Co(II) derivative with an uncharged macrocycle after the first controlled potential reduction of the nitro-substituted corroles. All four cobalt corroles were also examined as catalysts for the electroreduction of O2 when coated on an edge-plane pyrrolytic graphite electrode in 1.0 M HClO4. This study indicates that the larger the number of nitro-substituents on the cobalt corrole, the better the compound acts as a catalyst.