Intramolecular rearrangement for regioselective complexation by intramolecular CH/π interaction in a hydrophobic cavity of a ruthenium coordination sphere

Takahiko Kojima, Soushi Miyazaki, Ken Ichi Hayashi, Yuichi Shimazaki, Fumito Tani, Yoshinori Naruta, Yoshihisa Matsuda

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

A RuII complex with a hydrophobic cavity formed from two 1-naphthoylamide groups was prepared. Its reactions with β-diketones gave β-diketonato complexes in which hydrophobic π-π or CH/π interactions were confirmed by NMR spectroscopy and X-ray crystallography. In the case of the asymmetric β-diketone benzoylacetone, an isomer with a CH/π interaction was afforded as the sole product owing to thermodynamic control. The reaction was found to involve a novel intramolecular rearrangement from the phenyl-included isomer to the methyl-included one without rupture of Ru-β-diketonato coordination bonds (activation energy 52 kJ mol -1). This indicates that CH/π interactions can be more favored thermodynamically than π-π interactions in a suitable hydrophobic environment.

Original languageEnglish
Pages (from-to)6402-6410
Number of pages9
JournalChemistry - A European Journal
Volume10
Issue number24
DOIs
Publication statusPublished - Dec 3 2004

Fingerprint

Ruthenium
Complexation
Isomers
X ray crystallography
Nuclear magnetic resonance spectroscopy
Activation energy
Thermodynamics
benzoylacetone

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

Intramolecular rearrangement for regioselective complexation by intramolecular CH/π interaction in a hydrophobic cavity of a ruthenium coordination sphere. / Kojima, Takahiko; Miyazaki, Soushi; Hayashi, Ken Ichi; Shimazaki, Yuichi; Tani, Fumito; Naruta, Yoshinori; Matsuda, Yoshihisa.

In: Chemistry - A European Journal, Vol. 10, No. 24, 03.12.2004, p. 6402-6410.

Research output: Contribution to journalArticle

Kojima, Takahiko ; Miyazaki, Soushi ; Hayashi, Ken Ichi ; Shimazaki, Yuichi ; Tani, Fumito ; Naruta, Yoshinori ; Matsuda, Yoshihisa. / Intramolecular rearrangement for regioselective complexation by intramolecular CH/π interaction in a hydrophobic cavity of a ruthenium coordination sphere. In: Chemistry - A European Journal. 2004 ; Vol. 10, No. 24. pp. 6402-6410.
@article{85da1961d8094481ae822a72a7b643ff,
title = "Intramolecular rearrangement for regioselective complexation by intramolecular CH/π interaction in a hydrophobic cavity of a ruthenium coordination sphere",
abstract = "A RuII complex with a hydrophobic cavity formed from two 1-naphthoylamide groups was prepared. Its reactions with β-diketones gave β-diketonato complexes in which hydrophobic π-π or CH/π interactions were confirmed by NMR spectroscopy and X-ray crystallography. In the case of the asymmetric β-diketone benzoylacetone, an isomer with a CH/π interaction was afforded as the sole product owing to thermodynamic control. The reaction was found to involve a novel intramolecular rearrangement from the phenyl-included isomer to the methyl-included one without rupture of Ru-β-diketonato coordination bonds (activation energy 52 kJ mol -1). This indicates that CH/π interactions can be more favored thermodynamically than π-π interactions in a suitable hydrophobic environment.",
author = "Takahiko Kojima and Soushi Miyazaki and Hayashi, {Ken Ichi} and Yuichi Shimazaki and Fumito Tani and Yoshinori Naruta and Yoshihisa Matsuda",
year = "2004",
month = "12",
day = "3",
doi = "10.1002/chem.200400496",
language = "English",
volume = "10",
pages = "6402--6410",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "24",

}

TY - JOUR

T1 - Intramolecular rearrangement for regioselective complexation by intramolecular CH/π interaction in a hydrophobic cavity of a ruthenium coordination sphere

AU - Kojima, Takahiko

AU - Miyazaki, Soushi

AU - Hayashi, Ken Ichi

AU - Shimazaki, Yuichi

AU - Tani, Fumito

AU - Naruta, Yoshinori

AU - Matsuda, Yoshihisa

PY - 2004/12/3

Y1 - 2004/12/3

N2 - A RuII complex with a hydrophobic cavity formed from two 1-naphthoylamide groups was prepared. Its reactions with β-diketones gave β-diketonato complexes in which hydrophobic π-π or CH/π interactions were confirmed by NMR spectroscopy and X-ray crystallography. In the case of the asymmetric β-diketone benzoylacetone, an isomer with a CH/π interaction was afforded as the sole product owing to thermodynamic control. The reaction was found to involve a novel intramolecular rearrangement from the phenyl-included isomer to the methyl-included one without rupture of Ru-β-diketonato coordination bonds (activation energy 52 kJ mol -1). This indicates that CH/π interactions can be more favored thermodynamically than π-π interactions in a suitable hydrophobic environment.

AB - A RuII complex with a hydrophobic cavity formed from two 1-naphthoylamide groups was prepared. Its reactions with β-diketones gave β-diketonato complexes in which hydrophobic π-π or CH/π interactions were confirmed by NMR spectroscopy and X-ray crystallography. In the case of the asymmetric β-diketone benzoylacetone, an isomer with a CH/π interaction was afforded as the sole product owing to thermodynamic control. The reaction was found to involve a novel intramolecular rearrangement from the phenyl-included isomer to the methyl-included one without rupture of Ru-β-diketonato coordination bonds (activation energy 52 kJ mol -1). This indicates that CH/π interactions can be more favored thermodynamically than π-π interactions in a suitable hydrophobic environment.

UR - http://www.scopus.com/inward/record.url?scp=10944253667&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=10944253667&partnerID=8YFLogxK

U2 - 10.1002/chem.200400496

DO - 10.1002/chem.200400496

M3 - Article

C2 - 15532051

AN - SCOPUS:10944253667

VL - 10

SP - 6402

EP - 6410

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 24

ER -