Organocopper(III) Phenanthriporphyrin—Exocyclic Transformations

Abstract

phyrin 2 act as suitable organometallic ligands for copper(III), adopting trianionic [CCNN] coordination cores. Under oxidizing conditions, in the presence of methanol, copper(III) phenanthriporphyrin 1-Cu undergoes transformation to copper(III) phenanthriporphodimethene with methoxy substituents attached to two trans meso positions. Addition of acids to 1-Cu yields two isomeric copper(III) isophenanthriporphyrins protonated on one of the meso carbon atoms. Protonation of copper(III) 5,6-dioxophenanthriporphyrin 2-Cu yields the aromatic diprotonated complex 2-Cu-H 2 2+ . In the presence of HBF 4 2-Cu undergoes borylation at the carbonyl oxygen atoms, forming an aromatic exocyclic boron(III) complex.

Polycyclic Aromatic Hydrocarbon‐/Heterocycle‐Embedded Porphyrinoids

“…The authors also carried out the demethylation of antiaromatic macrocycle 40 by treating it with H 2 SO 4 to obtain a nonaromatic macrocycle 9,10dioxophenanthriporphyrin 45 in 70% yield. [26] Latos-Grażyński and co-workers synthesized Cu(III) complexes 40.Cu and 45.Cu by reacting 40 and 45 respectively with copper(II) acetate at reflux in o-chlorobenzene (Scheme 8 and 9). [26] The crystal structure of 40.Cu showed that Cu(III) ion was nearly in a square planar geometry and bound to two nitrogen atoms and two carbon atoms of the macrocyclic core.…”

“…The NICS(0) values at the centre of macrocycles were 12.1 ( 40 ) and 12.0 ( 40.H + ), which is consistent with the antiaromatic nature of macrocycles. The authors also carried out the demethylation of antiaromatic macrocycle 40 by treating it with H 2 SO 4 to obtain a nonaromatic macrocycle 9,10‐dioxophenanthriporphyrin 45 in 70% yield …”

“…Latos‐Grażyński and co‐workers synthesized Cu(III) complexes 40.Cu and 45.Cu by reacting 40 and 45 respectively with copper(II) acetate at reflux in o ‐chlorobenzene (Scheme and ) . The crystal structure of 40.Cu showed that Cu(III) ion was nearly in a square planar geometry and bound to two nitrogen atoms and two carbon atoms of the macrocyclic core.…”

Expanded Carbaporphyrinoids

“…The3 2-thia-5,6-dioxophenanthrisapphyrin 188 can be considered as the expanded congener of dioxophenanthriporphyrin. [150,151] Further extension of the phenanthrisapphyrin framework by consecutive incorporation of another heterocyclic unit together with alinked meso substituent yielded, instead of the expected phenanthrihexaphyrin(1.1.1.1.1.0), helicenophyrin 189 with an incorporated aza [5]helicene unit (Scheme 31). [152] Them acrocycle was obtained from am ixed condensation of phenanthritripyrrane,d ipyrromethane,a nd p-nitrobenzaldehyde under Lindsey reaction conditions.P henanthrihexaphyrin(1.1.1.1.1.0) was anticipated to be the initial macrocyclic product.…”

Expandierte Carbaporphyrinoide

“…Die schwache Paratropizitätvon 185 wurde vollständig ausgeschaltet, wenn zwei Methoxygruppen von 185 abgespalten wurden und folglich eine spontane Oxidation zum entsprechenden Dioxoderivat 188 erfolgte.Die 32-Thia-5,6-dioxophenanthrisapphyrine 188 kçnnen als erweiterte Kongenere von Dioxophenanthriporphyrin betrachtet werden. [150,151] Die weitere Verlängerung des Phenanthrisapphyrin-Gerüstes durch die konsekutive Einführung einer weiteren heterocyclischen Einheit zusammen mit einem meso-Substituenten führte,a nstatt zum erwarteten Phenanthrihexaphyrin(1.1.1.1.1.0), zum Helicenophyrin 189 mit einer eingebundenen Aza [5]helicen-Einheit (Schema 31). [152] Der Makrocyclus wurde in einer gemischten Kondensation von Phenanthritripyrran, Dipyrromethan und p-Nitrobenzaldehyd unter Lindsey-Reaktionsbedingungen erhalten.…”