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

研究成果: Article査読

54 被引用数 (Scopus)

抄録

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.

本文言語English
ページ(範囲)4396-4407
ページ数12
ジャーナルChemistry - A European Journal
17
16
DOI
出版ステータスPublished - 2011 4 11

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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