213481-27-7Relevant academic research and scientific papers
Oxidative Cyclodehydrogenation Reactions with Tetraarylporphyrins
Hampel, Frank,Jux, Norbert,Martin, Max M.,Oleszak, Christoph
, p. 6758 - 6762 (2020)
The extension of the aromatic π-system of porphyrins is a powerful method to alter their optoelectronic properties. Herein, aryl substituents were fused to porphyrin cores by Scholl oxidation reactions that selectively produced mono- and doubly-fused porphyrins in yields of up to 69 %. Several different aryl substituents attached to the porphyrin were investigated with respect to their reactivity under Scholl conditions. The fused products were fully characterized, i.e., by UV/Vis absorption spectroscopy, which showed drastic changes in the electronic features. Insight into the solid-state behavior was obtained by X-ray crystallography. Our approach represents a novel option for the late-stage functionalization of porphyrin-based compounds.
Synthesis, characterization, and electronic properties of metalloporphyrins annulated to exocyclic imidazole and imidazolium rings
Lefebvre, Jean-Francois,Leclercq, Dominique,Gisselbrecht, Jean-Paul,Richeter, Sebastien
scheme or table, p. 1912 - 1920 (2010/05/19)
meso-Tetraarylporphyrin complexes (M = Ni, Cu, Zn, H2) fused to an imidazole ring across two neighboring β-pyrrolic positions were synthesized through a cyclization reaction between β,β'- diaminoporphyrins and formic acid or trimethyl orthoformate under acidic conditions. Two synthetic procedures were used to obtain the corresponding porphyrin N,N'-dimethylimidazolium salts derivatives: alkylation of the imidazole nitrogen atoms with iodomethane and the cyclization reaction between the porphyrin bearing two neighboring β-N-methyl groups and trimethyl orthoformate in the presence of ammonium hexafluorophosphate. The electrochemical properties of these porphyrins annulated to an imidazole/imidazolium ring have been investigated by cyclic and rotating disk voltammetry.
Reactions of nitroxides with metalloporphyrin alkyls bearing beta hydrogens: Aliphatic carbon-carbon bond activation by metal centered radicals
Chan, Kin Shing,Mak, Kin Wah,Tse, Man Kin,Yeung, Siu Kwan,Li, Bao Zhu,Chan, Yun Wai
, p. 399 - 407 (2008/03/18)
Nitroxide-induced beta-hydrogen atom abstraction and beta-elimination of rhodium porphyrin alkyls have been observed. Rhodium(II) porphyrin radical were proposed intermediates to form first and subsequently reacted via aliphatic carbon-carbon bond activation with alkyl substituted nitroxides to yield rhodium porphyrin alkyl complexes.
