The synthesis and properties of free-base [14]triphyrin(2.1.1) compounds and the formation of subporphyrinoid metal complexes

Zhao Li Xue, John Mack, Hua Lu, Lei Zhang, Xiao Zeng You, Daiki Kuzuhara, Martin Stillman, Hiroko Yamada, Seigo Yamauchi, Nagao Kobayashi, Zhen Shen

Research output: Contribution to journalArticlepeer-review

53 Citations (Scopus)

Abstract

The synthesis of [14]triphyrin(2.1.1) compounds is described. In contrast with conventional subporphyrins, which consistently contain a central boron atom, free-base heteroaromatic compounds can be formed. A modified Lindsey method was used to prepare a range of different [14]triphyrins(2.1.1) in yields of up to 35% based on the reaction of diethylpyrrole (1a) and fused pyrroles of bicyclo[2.2.2]octadiene (BCOD) (2a-e) and dihydroethanonaphthalene (4a) with various aryl aldehydes. The concentration of BF3OEt2 catalyst plays the key role in determining the yield of the [14]triphyrin(2.1.1) macrocycle relative to the conventional tetrapyrrole porphyrin product. Retro-Diels-Alder reactions of 2a-e and 4a result in the formation of [14]tribenzotriphyrin (2.1.1) (3a-e) and [14]trinaphthotriphyrin(2.1.1) (5a). The effects of exocyclic ring annulation on the electronic structure are examined in detail based on optical spectroscopy, theoretical calculations, and electrochemical measurements. The availability of free-base compounds enables the formation of [ReI(CO)3(triphyrin)] (6a) and [Ru II(CO)2Cl(triphyrin)] (7a) complexes based on a modified retro-Diels-Alder reaction. X-ray structures are reported for 4a and 6a.

Original languageEnglish
Pages (from-to)4396-4407
Number of pages12
JournalChemistry - A European Journal
Volume17
Issue number16
DOIs
Publication statusPublished - 2011 Apr 11

Keywords

  • electrochemistry
  • magnetic circular dichroism
  • porphyrinoids
  • structure elucidation
  • triphyrins

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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