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Oxidative Formation and Redox Properties of 9‐Methylisocorroles
Author(s) -
Wicht Richard,
Bahnmüller Stefanie,
Thüsing Anne,
Wolfram Benedikt,
Bröring Martin
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201901037
Subject(s) - chemistry , corrole , tetrafluoroborate , redox , copper , photochemistry , nickel , nucleophile , radical , transition metal , metal , electrochemistry , yield (engineering) , electron transfer , inorganic chemistry , derivative (finance) , reductive elimination , oxidative addition , organic chemistry , catalysis , ionic liquid , materials science , electrode , economics , financial economics , metallurgy
Cationic nickel(II), palladium(II), and copper(II) isocorrole complexes were obtained from linear tetrapyrrolic 2,2′‐bidipyrrin precursors by metal‐templated oxidative macrocyclization reactions using silver(I) tetrafluoroborate as the oxidant in 40–69 % yield. The new compounds were characterized by optical and resonance methods. Two products from overoxidation and attack of nucleophiles were identified by means of single‐crystal X‐ray diffraction, elucidating possible H atom transfer processes during and after the macrocyclization step. The redox behavior was studied by UV/Vis‐spectroelectrochemistry, and the complexes were found to show different stabilities of the electrogenerated radicals, depending on the nature of the central transition metal ion. A one‐electron reduction step at low potential is common for all species, but reversible only in the case of nickel, and an irreversible reaction of a copper derivative was found to produce copper corrole.