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UO2 2+-mediated ring contraction of pyrihexaphyrin: synthesis of a contracted expanded porphyrin-uranyl complex.

ABSTRACT: A new mixed hexaphyrin, pyrihexaphyrin (0.1.0.0.1.0) (1), was prepared via an acid catalyzed cyclization between 5,5'-(pyridine-2,6-diyl)bis(pyrrole-2-carbaldehyde) (2) and terpyrrole (3). This expanded porphyrin undergoes a ring contraction upon metallation with uranyl silylamide [UO2[N(SiMe3)2]2] under anaerobic conditions followed by purification over basic aluminum oxide exposed to air. The uranyl-contracted pyrihexaphyrin (0.0.0.0.1.0) complex (4) produced as a result contains a unique structural architecture and possesses a formally 22 ?-electron globally aromatic periphery, as inferred from NMR spectroscopy, single crystal X-ray diffraction, and computational analyses. Support for the proposed contraction mechanism came from experimental data and DFT calculations. Proton NMR and mass spectroscopic analysis provided the first insight into expanded porphyrin-mediated activation of the uranyl dication (UO2 2+).

SUBMITTER: Brewster JT 

PROVIDER: S-EPMC6552508 | biostudies-literature | 2019 Jun

REPOSITORIES: biostudies-literature

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UO<sub>2</sub> <sup>2+</sup>-mediated ring contraction of pyrihexaphyrin: synthesis of a contracted expanded porphyrin-uranyl complex.

Brewster James T JT   Root Harrison D HD   Mangel Daniel D   Samia Adam A   Zafar Hadiqa H   Sedgwick Adam C AC   Lynch Vincent M VM   Sessler Jonathan L JL  

Chemical science 20190430 21

A new mixed hexaphyrin, pyrihexaphyrin (0.1.0.0.1.0) (<b>1</b>), was prepared <i>via</i> an acid catalyzed cyclization between 5,5'-(pyridine-2,6-diyl)bis(pyrrole-2-carbaldehyde) (<b>2</b>) and terpyrrole (<b>3</b>). This expanded porphyrin undergoes a ring contraction upon metallation with uranyl silylamide [UO<sub>2</sub>[N(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>] under anaerobic conditions followed by purification over basic aluminum oxide exposed to air. The uranyl-contracted pyrihexaphyr  ...[more]

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