Directly Diphenylborane-Fused Porphyrins

Keisuke Fujimoto, Juwon Oh, Hideki Yorimitsu, Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

Mono- and bis(diphenylborane)-fused porphyrins were synthesized from the corresponding β-(2-trimethylsilylphenyl)-substituted porphyrins through the sequence of Si–B exchange reaction, intramolecular bora-Friedel–Crafts reaction, and ring-closing Si–B exchange reaction. Effective electronic interactions of the empty p-orbital of the boron atom with the porphyrin π-circuit lead to red-shifted absorption spectra and substantially decreased LUMO energy levels. Pyridine adds at the boron center to cause disruption of the electronic interaction of the boron atom with large association constants (1.9–17×104 m−1) depending on the central metal at the porphyrin. The ZnII complex behaved as a hetero-dinuclear Lewis acid, exhibiting regioselective binding of pyridines at the boron or the zinc center.
Original languageEnglish
Pages (from-to)3196-3199
Number of pages4
JournalAngewandte Chemie - International Edition
Volume55
Issue number9
DOIs
Publication statusPublished - 2016 Feb 24

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Boron
Porphyrins
Pyridine
Pyridines
Lewis Acids
Atoms
Electron energy levels
Zinc
Absorption spectra
Metals
Acids
Networks (circuits)

Cite this

Fujimoto, Keisuke ; Oh, Juwon ; Yorimitsu, Hideki ; Kim, Dongho ; Osuka, Atsuhiro. / Directly Diphenylborane-Fused Porphyrins. In: Angewandte Chemie - International Edition. 2016 ; Vol. 55, No. 9. pp. 3196-3199.
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Fujimoto, K, Oh, J, Yorimitsu, H, Kim, D & Osuka, A 2016, 'Directly Diphenylborane-Fused Porphyrins', Angewandte Chemie - International Edition, vol. 55, no. 9, pp. 3196-3199. https://doi.org/10.1002/anie.201511981

Directly Diphenylborane-Fused Porphyrins. / Fujimoto, Keisuke; Oh, Juwon; Yorimitsu, Hideki; Kim, Dongho; Osuka, Atsuhiro.

In: Angewandte Chemie - International Edition, Vol. 55, No. 9, 24.02.2016, p. 3196-3199.

Research output: Contribution to journalArticle

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AU - Fujimoto, Keisuke

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AB - Mono- and bis(diphenylborane)-fused porphyrins were synthesized from the corresponding β-(2-trimethylsilylphenyl)-substituted porphyrins through the sequence of Si–B exchange reaction, intramolecular bora-Friedel–Crafts reaction, and ring-closing Si–B exchange reaction. Effective electronic interactions of the empty p-orbital of the boron atom with the porphyrin π-circuit lead to red-shifted absorption spectra and substantially decreased LUMO energy levels. Pyridine adds at the boron center to cause disruption of the electronic interaction of the boron atom with large association constants (1.9–17×104 m−1) depending on the central metal at the porphyrin. The ZnII complex behaved as a hetero-dinuclear Lewis acid, exhibiting regioselective binding of pyridines at the boron or the zinc center.

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