Oxatriphyrins(2.1.1) Incorporating an ortho‐Phenylene Motif1. Issue 6 (21st December 2014)

• Record Type: Journal Article
• Authors: Pawlicki, Miłosz; Garbicz, Mateusz; Szterenberg, Ludmiła; Latos‐Grażyński, Lechosław
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 6(2015)
• Page Start: 1906
• Page End: 1909
• Publication Date: 2014-12-21
• Subjects: aromaticity -- boron -- density functional calculations -- macrocycles -- structure elucidation; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201410595
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: An understanding of fundamental aspects of archetypal organic structural motifs remains a key issue faced by the experimental and theoretical chemists. Two possible bonding modes for a disubstituted benzene ring, that is a meta and para, determines the π delocalization for oligomeric structures. When the less abundant ortho ‐substituted variant is introduced into a triphyrin(2.1.1) skeleton an aromatic molecule is obtained and the carbocyclic ring participates in the conjugation of the macrocycle. The two‐electron reduction and introduction of boron(III) changes the aromatic character and results in an anti‐aromatic structure which has been confirmed by single‐crystal analysis and supported by theoretical calculations. Abstract : Staying close : Oxatriphyrin(2.1.1) incorporating an ortho ‐phenylene moiety leads to an aromatic compound in which the benzene fragment participates in π delocalization. The proximity of the heteroatoms (N, O, N) results in a strong intramolecular three‐centered hydrogen bond. The introduction of boron(III) leads to a complex having a paratropic current.