Theoretical study of oxidation of cyclohexane diol to adipic anhydride by [RuIV(O)(tpa)(H2O)]2+ complex (tpa = Tris(2-pyridylmethyl)amine)

Yoshihito Shiota, Jorge M. Herrera, Gergely Juhász, Takafumi Abe, Shingo Ohzu, Tomoya Ishizuka, Takahiko Kojima, Kazunari Yoshizawa

研究成果: ジャーナルへの寄稿記事

9 引用 (Scopus)

抄録

The catalytic conversion of 1,2-cyclohexanediol to adipic anhydride by RuIVO(tpa) (tpa = tris(2-pyridylmethyl)amine) is discussed using density functional theory calculations. The whole reaction is divided into three steps: (1) formation of α-hydroxy cyclohexanone by dehydrogenation of cyclohexanediol, (2) formation of 1,2-cyclohexanedione by dehydrogenation of α-hydroxy cyclohexanone, and (3) formation of adipic anhydride by oxygenation of cyclohexanedione. In each step the two-electron oxidation is performed by RuIVO(tpa) active species, which is reduced to bis-aqua RuII(tpa) complex. The RuII complex is reactivated using Ce(IV) and water as an oxygen source. There are two different pathways of the first two steps of the conversion depending on whether the direct H-atom abstraction occurs on a C-H bond or on its adjacent oxygen O-H. In the first step, the C-H (O-H) bond dissociation occurs in TS1 (TS2-1) with an activation barrier of 21.4 (21.6) kcal/mol, which is followed by abstraction of another hydrogen with the spin transition in both pathways. The second process also bifurcates into two reaction pathways. TS3 (TS4-1) is leading to dissociation of the C-H (O-H) bond, and the activation barrier of TS3 (TS4-1) is 20.2 (20.7) kcal/mol. In the third step, oxo ligand attack on the carbonyl carbon and hydrogen migration from the water ligand occur via TS5 with an activation barrier of 17.4 kcal/mol leading to a stable tetrahedral intermediate in a triplet state. However, the slightly higher energy singlet state of this tetrahedral intermediate is unstable; therefore, a spin crossover spontaneously transforms the tetrahedral intermediate into a dione complex by a hydrogen rebound and a C-C bond cleavage. Kinetic isotope effects (kH/k D) for the electronic processes of the C-H bond dissociations calculated to be 4.9-7.4 at 300 K are in good agreement with experiment values of 2.8-9.0.

元の言語英語
ページ(範囲)6200-6209
ページ数10
ジャーナルInorganic Chemistry
50
発行部数13
DOI
出版物ステータス出版済み - 7 4 2011

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Anhydrides
anhydrides
cyclohexane
Hydrogen
amines
Chemical activation
Dehydrogenation
Oxidation
oxidation
Oxygen
Ligands
activation
dissociation
dehydrogenation
Oxygenation
Water
Isotopes
hydrogen
Electron energy levels
Density functional theory

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

これを引用

Theoretical study of oxidation of cyclohexane diol to adipic anhydride by [RuIV(O)(tpa)(H2O)]2+ complex (tpa = Tris(2-pyridylmethyl)amine). / Shiota, Yoshihito; Herrera, Jorge M.; Juhász, Gergely; Abe, Takafumi; Ohzu, Shingo; Ishizuka, Tomoya; Kojima, Takahiko; Yoshizawa, Kazunari.

:: Inorganic Chemistry, 巻 50, 番号 13, 04.07.2011, p. 6200-6209.

研究成果: ジャーナルへの寄稿記事

Shiota, Yoshihito ; Herrera, Jorge M. ; Juhász, Gergely ; Abe, Takafumi ; Ohzu, Shingo ; Ishizuka, Tomoya ; Kojima, Takahiko ; Yoshizawa, Kazunari. / Theoretical study of oxidation of cyclohexane diol to adipic anhydride by [RuIV(O)(tpa)(H2O)]2+ complex (tpa = Tris(2-pyridylmethyl)amine). :: Inorganic Chemistry. 2011 ; 巻 50, 番号 13. pp. 6200-6209.
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title = "Theoretical study of oxidation of cyclohexane diol to adipic anhydride by [RuIV(O)(tpa)(H2O)]2+ complex (tpa = Tris(2-pyridylmethyl)amine)",
abstract = "The catalytic conversion of 1,2-cyclohexanediol to adipic anhydride by RuIVO(tpa) (tpa = tris(2-pyridylmethyl)amine) is discussed using density functional theory calculations. The whole reaction is divided into three steps: (1) formation of α-hydroxy cyclohexanone by dehydrogenation of cyclohexanediol, (2) formation of 1,2-cyclohexanedione by dehydrogenation of α-hydroxy cyclohexanone, and (3) formation of adipic anhydride by oxygenation of cyclohexanedione. In each step the two-electron oxidation is performed by RuIVO(tpa) active species, which is reduced to bis-aqua RuII(tpa) complex. The RuII complex is reactivated using Ce(IV) and water as an oxygen source. There are two different pathways of the first two steps of the conversion depending on whether the direct H-atom abstraction occurs on a C-H bond or on its adjacent oxygen O-H. In the first step, the C-H (O-H) bond dissociation occurs in TS1 (TS2-1) with an activation barrier of 21.4 (21.6) kcal/mol, which is followed by abstraction of another hydrogen with the spin transition in both pathways. The second process also bifurcates into two reaction pathways. TS3 (TS4-1) is leading to dissociation of the C-H (O-H) bond, and the activation barrier of TS3 (TS4-1) is 20.2 (20.7) kcal/mol. In the third step, oxo ligand attack on the carbonyl carbon and hydrogen migration from the water ligand occur via TS5 with an activation barrier of 17.4 kcal/mol leading to a stable tetrahedral intermediate in a triplet state. However, the slightly higher energy singlet state of this tetrahedral intermediate is unstable; therefore, a spin crossover spontaneously transforms the tetrahedral intermediate into a dione complex by a hydrogen rebound and a C-C bond cleavage. Kinetic isotope effects (kH/k D) for the electronic processes of the C-H bond dissociations calculated to be 4.9-7.4 at 300 K are in good agreement with experiment values of 2.8-9.0.",
author = "Yoshihito Shiota and Herrera, {Jorge M.} and Gergely Juh{\'a}sz and Takafumi Abe and Shingo Ohzu and Tomoya Ishizuka and Takahiko Kojima and Kazunari Yoshizawa",
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T1 - Theoretical study of oxidation of cyclohexane diol to adipic anhydride by [RuIV(O)(tpa)(H2O)]2+ complex (tpa = Tris(2-pyridylmethyl)amine)

AU - Shiota, Yoshihito

AU - Herrera, Jorge M.

AU - Juhász, Gergely

AU - Abe, Takafumi

AU - Ohzu, Shingo

AU - Ishizuka, Tomoya

AU - Kojima, Takahiko

AU - Yoshizawa, Kazunari

PY - 2011/7/4

Y1 - 2011/7/4

N2 - The catalytic conversion of 1,2-cyclohexanediol to adipic anhydride by RuIVO(tpa) (tpa = tris(2-pyridylmethyl)amine) is discussed using density functional theory calculations. The whole reaction is divided into three steps: (1) formation of α-hydroxy cyclohexanone by dehydrogenation of cyclohexanediol, (2) formation of 1,2-cyclohexanedione by dehydrogenation of α-hydroxy cyclohexanone, and (3) formation of adipic anhydride by oxygenation of cyclohexanedione. In each step the two-electron oxidation is performed by RuIVO(tpa) active species, which is reduced to bis-aqua RuII(tpa) complex. The RuII complex is reactivated using Ce(IV) and water as an oxygen source. There are two different pathways of the first two steps of the conversion depending on whether the direct H-atom abstraction occurs on a C-H bond or on its adjacent oxygen O-H. In the first step, the C-H (O-H) bond dissociation occurs in TS1 (TS2-1) with an activation barrier of 21.4 (21.6) kcal/mol, which is followed by abstraction of another hydrogen with the spin transition in both pathways. The second process also bifurcates into two reaction pathways. TS3 (TS4-1) is leading to dissociation of the C-H (O-H) bond, and the activation barrier of TS3 (TS4-1) is 20.2 (20.7) kcal/mol. In the third step, oxo ligand attack on the carbonyl carbon and hydrogen migration from the water ligand occur via TS5 with an activation barrier of 17.4 kcal/mol leading to a stable tetrahedral intermediate in a triplet state. However, the slightly higher energy singlet state of this tetrahedral intermediate is unstable; therefore, a spin crossover spontaneously transforms the tetrahedral intermediate into a dione complex by a hydrogen rebound and a C-C bond cleavage. Kinetic isotope effects (kH/k D) for the electronic processes of the C-H bond dissociations calculated to be 4.9-7.4 at 300 K are in good agreement with experiment values of 2.8-9.0.

AB - The catalytic conversion of 1,2-cyclohexanediol to adipic anhydride by RuIVO(tpa) (tpa = tris(2-pyridylmethyl)amine) is discussed using density functional theory calculations. The whole reaction is divided into three steps: (1) formation of α-hydroxy cyclohexanone by dehydrogenation of cyclohexanediol, (2) formation of 1,2-cyclohexanedione by dehydrogenation of α-hydroxy cyclohexanone, and (3) formation of adipic anhydride by oxygenation of cyclohexanedione. In each step the two-electron oxidation is performed by RuIVO(tpa) active species, which is reduced to bis-aqua RuII(tpa) complex. The RuII complex is reactivated using Ce(IV) and water as an oxygen source. There are two different pathways of the first two steps of the conversion depending on whether the direct H-atom abstraction occurs on a C-H bond or on its adjacent oxygen O-H. In the first step, the C-H (O-H) bond dissociation occurs in TS1 (TS2-1) with an activation barrier of 21.4 (21.6) kcal/mol, which is followed by abstraction of another hydrogen with the spin transition in both pathways. The second process also bifurcates into two reaction pathways. TS3 (TS4-1) is leading to dissociation of the C-H (O-H) bond, and the activation barrier of TS3 (TS4-1) is 20.2 (20.7) kcal/mol. In the third step, oxo ligand attack on the carbonyl carbon and hydrogen migration from the water ligand occur via TS5 with an activation barrier of 17.4 kcal/mol leading to a stable tetrahedral intermediate in a triplet state. However, the slightly higher energy singlet state of this tetrahedral intermediate is unstable; therefore, a spin crossover spontaneously transforms the tetrahedral intermediate into a dione complex by a hydrogen rebound and a C-C bond cleavage. Kinetic isotope effects (kH/k D) for the electronic processes of the C-H bond dissociations calculated to be 4.9-7.4 at 300 K are in good agreement with experiment values of 2.8-9.0.

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