Two Discrete RuCp* (Cp*=Pentamethylcyclopentadienyl) Binding Modes of N-Confused Porphyrins

Peripheral π Complex and Sitting Atop Ruthenocenophane Complex by Skeletal Transformation

Takaaki Yamamoto, Koki Mitsuno, Shigeki Mori, Shuhei Itoyama, Yoshihito Shiota, Kazunari Yoshizawa, Masatoshi Ishida, Hiroyuki Furuta

Research output: Contribution to journalArticle

Abstract

Complexation of a RuCp* cation with N-confused tetraarylporphyrins (NCPs) forms directly bound ruthenium(II) pentamethylcyclopentadienyl (Cp*) π-complex on a specific meso-aryl group (e.g., phenyl) neighboring peripheral imino nitrogen of NCPs in high yields. In contrast, in the case of NCPs bearing bulky meso-substituents (e.g., 3,5-di-tert-butylphenyl), new ruthenocenophane-like complex embedded on an N-confused calix[4]phyrin was formed through multiple C−H bond activation of methyl groups of Cp* ligand. The mechanistic insight into the formation of the ruthenocenophane was derived from DFT calculations.

Original languageEnglish
Pages (from-to)6742-6746
Number of pages5
JournalChemistry - A European Journal
Volume24
Issue number26
DOIs
Publication statusPublished - May 7 2018

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Bearings (structural)
Ruthenium
Porphyrins
Complexation
Discrete Fourier transforms
Cations
Nitrogen
Positive ions
Chemical activation
Ligands

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

@article{d71283eee7544f0bb4cbe824bd532cf1,
title = "Two Discrete RuCp* (Cp*=Pentamethylcyclopentadienyl) Binding Modes of N-Confused Porphyrins: Peripheral π Complex and Sitting Atop Ruthenocenophane Complex by Skeletal Transformation",
abstract = "Complexation of a RuCp* cation with N-confused tetraarylporphyrins (NCPs) forms directly bound ruthenium(II) pentamethylcyclopentadienyl (Cp*) π-complex on a specific meso-aryl group (e.g., phenyl) neighboring peripheral imino nitrogen of NCPs in high yields. In contrast, in the case of NCPs bearing bulky meso-substituents (e.g., 3,5-di-tert-butylphenyl), new ruthenocenophane-like complex embedded on an N-confused calix[4]phyrin was formed through multiple C−H bond activation of methyl groups of Cp* ligand. The mechanistic insight into the formation of the ruthenocenophane was derived from DFT calculations.",
author = "Takaaki Yamamoto and Koki Mitsuno and Shigeki Mori and Shuhei Itoyama and Yoshihito Shiota and Kazunari Yoshizawa and Masatoshi Ishida and Hiroyuki Furuta",
year = "2018",
month = "5",
day = "7",
doi = "10.1002/chem.201801237",
language = "English",
volume = "24",
pages = "6742--6746",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "26",

}

TY - JOUR

T1 - Two Discrete RuCp* (Cp*=Pentamethylcyclopentadienyl) Binding Modes of N-Confused Porphyrins

T2 - Peripheral π Complex and Sitting Atop Ruthenocenophane Complex by Skeletal Transformation

AU - Yamamoto, Takaaki

AU - Mitsuno, Koki

AU - Mori, Shigeki

AU - Itoyama, Shuhei

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Ishida, Masatoshi

AU - Furuta, Hiroyuki

PY - 2018/5/7

Y1 - 2018/5/7

N2 - Complexation of a RuCp* cation with N-confused tetraarylporphyrins (NCPs) forms directly bound ruthenium(II) pentamethylcyclopentadienyl (Cp*) π-complex on a specific meso-aryl group (e.g., phenyl) neighboring peripheral imino nitrogen of NCPs in high yields. In contrast, in the case of NCPs bearing bulky meso-substituents (e.g., 3,5-di-tert-butylphenyl), new ruthenocenophane-like complex embedded on an N-confused calix[4]phyrin was formed through multiple C−H bond activation of methyl groups of Cp* ligand. The mechanistic insight into the formation of the ruthenocenophane was derived from DFT calculations.

AB - Complexation of a RuCp* cation with N-confused tetraarylporphyrins (NCPs) forms directly bound ruthenium(II) pentamethylcyclopentadienyl (Cp*) π-complex on a specific meso-aryl group (e.g., phenyl) neighboring peripheral imino nitrogen of NCPs in high yields. In contrast, in the case of NCPs bearing bulky meso-substituents (e.g., 3,5-di-tert-butylphenyl), new ruthenocenophane-like complex embedded on an N-confused calix[4]phyrin was formed through multiple C−H bond activation of methyl groups of Cp* ligand. The mechanistic insight into the formation of the ruthenocenophane was derived from DFT calculations.

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U2 - 10.1002/chem.201801237

DO - 10.1002/chem.201801237

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