Synthesis and properties of directly linked corrole–ferrocene systems

Abstract

Meso-substituted corroles bearing directly linked ferrocene unit have been synthesized for the first time. Among various methods studied, only the condensation of pentafluorophenyldipyrromethane with a formylferrocene led to this type of product. A triad containing corrole and porphyrin bridged with ferrocene has been obtained by a convergent approach. Bilanes were used as crucial substrates in the porphyrin-forming step. For the first time it was shown that H 2 O-MeOH-HCl conditions are suitable for preparation of various 10-(formylaryl)corroles via the direct condensation of aromatic dialdehydes with dipyrromethanes. Electrochemical studies of 10-ferrocenyl-5,15-bis(pentafluorophenyl)corrole support the possibility of intramolecular electron transfer from the corrole to the ferrocene system after the electrode oxidation of the ferrocene to a ferrocenium cation. We have studied the structure of 1-(corrolyl)-1 0 -(porphyrinyl)ferrocene by 1 H NMR and UV-Vis. NMR spectra show that this compound has more conformational freedom than analogous, previously studied bis-porphyrinylferrocenes. Absorption spectra suggest the lack of strong electronic interaction between ferrocene and porphyrinoids for dyads and significant conjugation for the triad.

Ferrocene-appended porphyrins: Syntheses and properties

“…Surprisingly, the reversibility of the ferrocene centred process turned out to be improved at lower scan rates as a possible consequence of a conformational re-arrangement which occurs at the time scale of the low scan rates. Following a similar strategy, the same authors reported an original pacman-type ferrocene bridged porphyrin-corrole in which the metallocene fragment is directly linked to both macrocycles [39]. NMR and UV-vis investigations on the latter revealed an improved conformational freedom compared to the bis-porphyrin analogue 21H 2 , and a poor electronic interaction between the ferrocene and corrole fragments.…”

“…The potential applications of these new architectures are similar to those mentioned in the previous paragraphs and rely on the exciting binding, electronic, structural properties of original macrocycles with various sizes, conjugation and heteroatoms. This field is rapidly growing and numerous examples have been recently reported with analogues as oxasmaragdyrin [101,102], corroles [39], oxacorroles [101], porphodimethenes [34,117], tetraazaporphyrins and phthalocyanines [51,53,[103][104][105][106][107][108][109][110] and others [111][112][113]. Some of these structures are depicted in Fig.…”

Palladium-catalyzed reaction of 2-iodoferrocenyl alcohols with internal alkynes: Synthesis of functionally 1,2-disubstituted ferrocenes and ferroceno-pyrans

“…Firstly, acetylferrocene (16) was reduced to ferrocenylethanol 17 by LiAlH 4 , and then the esterification of alcohol 17 with acetic anhydride produced acetate 18 quantitatively. The reaction of acetate 18 with dimethylamine in methanol at room temperature for 19 h gave N,Ndimethylaminoethylferrocene (19) in 93% yield. The key compound 2-(N,N-dimethylaminoethyl)iodoferrocene (20) was obtained as an only diastereomer in 62% yield by ortho-lithiation of 19 with secBuLi followed by iodination.…”

Efficient Two‐Step Synthesis of Face‐to‐Face meso‐Substituted Bis(corrole) Dyads

“…In addition to this work, linear bis(corrole)s and porphyrin-corrole dyads have also been reported by other groups. [37][38][39][40][41] Up to now, several homo-and heterobimetallic derivatives exhibiting interesting ligand binding properties have been synthesized and characterized by X-ray diffraction, spectroscopic techniques, and electrochemistry. [27][28][29]33,[42][43][44] The ability of bis(cobalt) complexes of porphyrin-corrole and bis(corrole) dyads to catalyze efficiently the reduction of oxygen to water was more interesting.…”