Ruthenium N-Confused Porphyrins

Selective Reactivity for Ambident 2-Heteroatom-Substituted Pyridines Serving as Axial Ligands

Takaaki Miyazaki, Kazuki Fukuyama, Shunichi Mashita, Yuya Deguchi, Takaaki Yamamoto, Masatoshi Ishida, Shigeki Mori, Hiroyuki Furuta

Research output: Contribution to journalArticle

Abstract

Three types of ruthenium(II) N-confused porphyrin (NCP) complexes bearing an axial 2-thiopyridine, 2-pyridone, and 2-iminopyridine moiety at the inner carbon atom, respectively, were synthesized. The unique reactivity of the 2-substituted pyridine derivatives (2-X-pyridine; X=SH, OH, NH2) toward the inner carbon atom of the NCP allows the formation of two types of coordinated products (i. e., pyridine donor versus 2-heteroatom donors), as inferred from single-crystal X-ray structures. The selective reactivity was investigated by using density functional theory (DFT) calculations. Finally, the catalytic activity of these ruthenium complexes was demonstrated through the styrene oxidation reactions. As a result, the ruthenium(II) NCP complex bearing a 2-thiopyridine moiety, together with aqueous H2O2 as an oxidant showed the highest selectivity for benzaldehyde (benzaldehyde/styrene oxide=20 : 1).

Original languageEnglish
Pages (from-to)603-607
Number of pages5
JournalChemPlusChem
Volume84
Issue number6
DOIs
Publication statusPublished - Jun 1 2019

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Pyridines
Ruthenium
Porphyrins
Bearings (structural)
styrene oxide
Ligands
Carbon
Atoms
Styrene
Oxidants
Density functional theory
Catalyst activity
Single crystals
Derivatives
X rays
Oxidation
pyridine
benzaldehyde
2-thiopyridine

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Ruthenium N-Confused Porphyrins : Selective Reactivity for Ambident 2-Heteroatom-Substituted Pyridines Serving as Axial Ligands. / Miyazaki, Takaaki; Fukuyama, Kazuki; Mashita, Shunichi; Deguchi, Yuya; Yamamoto, Takaaki; Ishida, Masatoshi; Mori, Shigeki; Furuta, Hiroyuki.

In: ChemPlusChem, Vol. 84, No. 6, 01.06.2019, p. 603-607.

Research output: Contribution to journalArticle

Miyazaki, Takaaki ; Fukuyama, Kazuki ; Mashita, Shunichi ; Deguchi, Yuya ; Yamamoto, Takaaki ; Ishida, Masatoshi ; Mori, Shigeki ; Furuta, Hiroyuki. / Ruthenium N-Confused Porphyrins : Selective Reactivity for Ambident 2-Heteroatom-Substituted Pyridines Serving as Axial Ligands. In: ChemPlusChem. 2019 ; Vol. 84, No. 6. pp. 603-607.
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abstract = "Three types of ruthenium(II) N-confused porphyrin (NCP) complexes bearing an axial 2-thiopyridine, 2-pyridone, and 2-iminopyridine moiety at the inner carbon atom, respectively, were synthesized. The unique reactivity of the 2-substituted pyridine derivatives (2-X-pyridine; X=SH, OH, NH2) toward the inner carbon atom of the NCP allows the formation of two types of coordinated products (i. e., pyridine donor versus 2-heteroatom donors), as inferred from single-crystal X-ray structures. The selective reactivity was investigated by using density functional theory (DFT) calculations. Finally, the catalytic activity of these ruthenium complexes was demonstrated through the styrene oxidation reactions. As a result, the ruthenium(II) NCP complex bearing a 2-thiopyridine moiety, together with aqueous H2O2 as an oxidant showed the highest selectivity for benzaldehyde (benzaldehyde/styrene oxide=20 : 1).",
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