Theoretical Study of the Catalytic Hydrogenation of Alkenes by a Disilaferracyclic Complex

Can the Fe-Si σ-Bond-Assisted Activation of H-H Bonds Allow Development of a Catalysis of Iron?

研究成果: ジャーナルへの寄稿記事

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The mechanisms associated with the hydrogenation of alkenes catalyzed by the iron complex Fe(cis-CO) 2 {o-(SiMe 2 ) 2 C 6 H 4 } 2 (H) 2 (1) were investigated by DFT calculations. The complex 1 has a structure in which the iron center is bonded to four silicon atoms and two hydrides. Secondary Si···H···Si interactions were also observed. The exchange of a 1,2-bis(dimethylsilyl)benzene ligand with ethylene and hydrogen gives a disilaferracycle bearing η 2 -(CH 2 =CH 2 ) and η 2 -H 2 ligands. The catalytic cycle initiated from the disilaferracycle involves cleavage of a H-H linkage assisted by an Fe-Si bond to form Fe-H and η 1 -(H-Si) moieties (step 1), hydrogen migration from the Fe-H group to the η 2 -(CH 2 =CH 2 ) ligand which accomplishes the insertion of ethylene into the Fe-H bond (step 2), and reaction of the resulting β-agostic ethyl moiety with the η 2 -(H-Si) group to form ethane on the iron atom (step 3). The octahedral geometry of 1 as well as the presence of π-acidic CO ligands and Fe-Si σ-bonds contributes to all of the catalytic intermediates and the transition states being in the low-spin state. Steps 1 and 3 correspond to the σ-complex-assisted metathesis (σ-CAM) mechanisms proposed by Perutz and Sabo-Etienne, suggesting that these mechanisms can assist in the design of iron-based hydrogenation catalysts operating under mild conditions.

元の言語英語
ページ(範囲)10900-10911
ページ数12
ジャーナルJournal of Organic Chemistry
81
発行部数22
DOI
出版物ステータス出版済み - 11 18 2016

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Alkenes
Catalysis
Hydrogenation
Iron
Chemical activation
Ligands
Carbon Monoxide
Hydrogen
Bearings (structural)
Atoms
Ethane
Silicon
Benzene
Discrete Fourier transforms
Hydrides
Catalysts
Geometry
ethylene

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

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title = "Theoretical Study of the Catalytic Hydrogenation of Alkenes by a Disilaferracyclic Complex: Can the Fe-Si σ-Bond-Assisted Activation of H-H Bonds Allow Development of a Catalysis of Iron?",
abstract = "The mechanisms associated with the hydrogenation of alkenes catalyzed by the iron complex Fe(cis-CO) 2 {o-(SiMe 2 ) 2 C 6 H 4 } 2 (H) 2 (1) were investigated by DFT calculations. The complex 1 has a structure in which the iron center is bonded to four silicon atoms and two hydrides. Secondary Si···H···Si interactions were also observed. The exchange of a 1,2-bis(dimethylsilyl)benzene ligand with ethylene and hydrogen gives a disilaferracycle bearing η 2 -(CH 2 =CH 2 ) and η 2 -H 2 ligands. The catalytic cycle initiated from the disilaferracycle involves cleavage of a H-H linkage assisted by an Fe-Si bond to form Fe-H and η 1 -(H-Si) moieties (step 1), hydrogen migration from the Fe-H group to the η 2 -(CH 2 =CH 2 ) ligand which accomplishes the insertion of ethylene into the Fe-H bond (step 2), and reaction of the resulting β-agostic ethyl moiety with the η 2 -(H-Si) group to form ethane on the iron atom (step 3). The octahedral geometry of 1 as well as the presence of π-acidic CO ligands and Fe-Si σ-bonds contributes to all of the catalytic intermediates and the transition states being in the low-spin state. Steps 1 and 3 correspond to the σ-complex-assisted metathesis (σ-CAM) mechanisms proposed by Perutz and Sabo-Etienne, suggesting that these mechanisms can assist in the design of iron-based hydrogenation catalysts operating under mild conditions.",
author = "Atsushi Tahara and Hiromasa Tanaka and Yusuke Sunada and Yoshihito Shiota and Kazunari Yoshizawa and Hideo Nagashima",
year = "2016",
month = "11",
day = "18",
doi = "10.1021/acs.joc.6b01961",
language = "English",
volume = "81",
pages = "10900--10911",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "22",

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TY - JOUR

T1 - Theoretical Study of the Catalytic Hydrogenation of Alkenes by a Disilaferracyclic Complex

T2 - Can the Fe-Si σ-Bond-Assisted Activation of H-H Bonds Allow Development of a Catalysis of Iron?

AU - Tahara, Atsushi

AU - Tanaka, Hiromasa

AU - Sunada, Yusuke

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Nagashima, Hideo

PY - 2016/11/18

Y1 - 2016/11/18

N2 - The mechanisms associated with the hydrogenation of alkenes catalyzed by the iron complex Fe(cis-CO) 2 {o-(SiMe 2 ) 2 C 6 H 4 } 2 (H) 2 (1) were investigated by DFT calculations. The complex 1 has a structure in which the iron center is bonded to four silicon atoms and two hydrides. Secondary Si···H···Si interactions were also observed. The exchange of a 1,2-bis(dimethylsilyl)benzene ligand with ethylene and hydrogen gives a disilaferracycle bearing η 2 -(CH 2 =CH 2 ) and η 2 -H 2 ligands. The catalytic cycle initiated from the disilaferracycle involves cleavage of a H-H linkage assisted by an Fe-Si bond to form Fe-H and η 1 -(H-Si) moieties (step 1), hydrogen migration from the Fe-H group to the η 2 -(CH 2 =CH 2 ) ligand which accomplishes the insertion of ethylene into the Fe-H bond (step 2), and reaction of the resulting β-agostic ethyl moiety with the η 2 -(H-Si) group to form ethane on the iron atom (step 3). The octahedral geometry of 1 as well as the presence of π-acidic CO ligands and Fe-Si σ-bonds contributes to all of the catalytic intermediates and the transition states being in the low-spin state. Steps 1 and 3 correspond to the σ-complex-assisted metathesis (σ-CAM) mechanisms proposed by Perutz and Sabo-Etienne, suggesting that these mechanisms can assist in the design of iron-based hydrogenation catalysts operating under mild conditions.

AB - The mechanisms associated with the hydrogenation of alkenes catalyzed by the iron complex Fe(cis-CO) 2 {o-(SiMe 2 ) 2 C 6 H 4 } 2 (H) 2 (1) were investigated by DFT calculations. The complex 1 has a structure in which the iron center is bonded to four silicon atoms and two hydrides. Secondary Si···H···Si interactions were also observed. The exchange of a 1,2-bis(dimethylsilyl)benzene ligand with ethylene and hydrogen gives a disilaferracycle bearing η 2 -(CH 2 =CH 2 ) and η 2 -H 2 ligands. The catalytic cycle initiated from the disilaferracycle involves cleavage of a H-H linkage assisted by an Fe-Si bond to form Fe-H and η 1 -(H-Si) moieties (step 1), hydrogen migration from the Fe-H group to the η 2 -(CH 2 =CH 2 ) ligand which accomplishes the insertion of ethylene into the Fe-H bond (step 2), and reaction of the resulting β-agostic ethyl moiety with the η 2 -(H-Si) group to form ethane on the iron atom (step 3). The octahedral geometry of 1 as well as the presence of π-acidic CO ligands and Fe-Si σ-bonds contributes to all of the catalytic intermediates and the transition states being in the low-spin state. Steps 1 and 3 correspond to the σ-complex-assisted metathesis (σ-CAM) mechanisms proposed by Perutz and Sabo-Etienne, suggesting that these mechanisms can assist in the design of iron-based hydrogenation catalysts operating under mild conditions.

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U2 - 10.1021/acs.joc.6b01961

DO - 10.1021/acs.joc.6b01961

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JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 22

ER -