title: Triphenylsilane-fused Porphyrins.
abstract: A reaction sequence of 2-(diphenylsilyl)phenylation by Negishi coupling and intramolecular sila-Friedel-Crafts reaction has been explored for the synthesis of mono-triphenylsilane-fused porphyrins 5 M and 6 M (M= Ni, Zn) and bis-triphenylsilane-fused porphyrins 7 M and 8 Ni. A triply linked triphenylsilane-fused Ni(II) porphyrin, 13 Ni, was synthesized in a stepwise manner involving the above reaction sequence and a final Pd-catalyzed C-H activating arylative cyclization. The silicon atom in 13 Ni takes a distorted planarized structure with an almost perpendicular Si-phenyl group, causing an electronic effect due to effective σ*-π* interaction.
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.
authors.forename: Kenichi
authors.initials: K
authors.lastname: Kato
authors.affiliation: Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749, Korea.
authors.forename: Jun Oh
authors.initials: JO
authors.lastname: Kim
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan. yori@kuchem.kyoto-u.ac.jp.
authors.forename: Hideki
authors.initials: H
authors.lastname: Yorimitsu
authors.affiliation: Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749, Korea. dongho@yonsei.ac.kr.
authors.forename: Dongho
authors.initials: D
authors.lastname: Kim
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan. osuka@kuchem.kyoto-u.ac.jp.
authors.forename: Atsuhiro
authors.initials: A
authors.lastname: Osuka
keywords: electrophilic substitution; fused-ring systems; porphyrinoids; sila-Friedel-Crafts reaction; silicon