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Porphyrin‐Stabilized Nitrenium Dication
Author(s) -
Fujimoto Keisuke,
Shimizu Daiki,
Osuka Atsuhiro
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201805491
Subject(s) - dication , chemistry , porphyrin , dimer , photochemistry , amination , aryl , diradical , medicinal chemistry , ion , organic chemistry , alkyl , physics , nuclear physics , singlet state , excited state , catalysis
An azepine‐fused Ni II ‐porphyrin dimer was synthesized by oxidative amination of β–β linked Ni II ‐porphyrin dimer, and its N ‐aryl congener was synthesized by twofold Buchwald–Hartwig amination of β‐to‐β linked and dichlorinated Ni II ‐porphyrin dimer. Oxidation of the NH congener gave neutral aminyl radical and nitrenium ion successively in a similar manner to the previously reported NH‐bridged Ni II ‐porphyrin dimer. Oxidation of the N ‐aryl congener afforded formal nitrenium dication in a single‐step two‐electron oxidation. Stable nitrenium dications that are isoelectronic to neutral trivalent boron compounds and tertiary carbocations are rare. The chemical stability of the nitrenium dication was improved by chlorine substitution at the most reactive β‐position. The structural, optical, magnetic, electrochemical properties of these compounds were fully characterized.