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 language | English |
|---|---|
| Pages (from-to) | 603-607 |
| Number of pages | 5 |
| Journal | ChemPlusChem |
| Volume | 84 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - Jun 1 2019 |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
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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 journal › Article
}
TY - JOUR
T1 - Ruthenium N-Confused Porphyrins
T2 - Selective Reactivity for Ambident 2-Heteroatom-Substituted Pyridines Serving as Axial Ligands
AU - Miyazaki, Takaaki
AU - Fukuyama, Kazuki
AU - Mashita, Shunichi
AU - Deguchi, Yuya
AU - Yamamoto, Takaaki
AU - Ishida, Masatoshi
AU - Mori, Shigeki
AU - Furuta, Hiroyuki
PY - 2019/6/1
Y1 - 2019/6/1
N2 - 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).
AB - 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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U2 - 10.1002/cplu.201800630
DO - 10.1002/cplu.201800630
M3 - Article
VL - 84
SP - 603
EP - 607
JO - ChemPlusChem
JF - ChemPlusChem
SN - 2192-6506
IS - 6
ER -