Theoretical Study on the Rhodium-Catalyzed Hydrosilylation of C=C and C=O Double Bonds with Tertiary Silane

Liming Zhao, Naoki Nakatani, Yusuke Sunada, Hideo Nagashima, Jun Ya Hasegawa

研究成果: ジャーナルへの寄稿記事

抄録

Reaction mechanisms of hydrosilylation of ketone and alkene with tertiary silane using the Wilkinson-type catalyst were theoretically investigated on the basis of density functional calculations using ωB97XD functional. Previously proposed three mechanisms, the Chalk-Harrod (CH) mechanism, the modified Chalk-Harrod (mCH) mechanism, and the outer-sphere mechanism were examined. Besides, we also found two mechanisms, the alternative CH (aCH) mechanism and the double hydride (DH) mechanism. In the aCH mechanism, a four-coordinate rhodium hydride complex formed through the elimination of R3Si-Cl is a catalytically active species. In the DH mechanism, the active species is a six-coordinate complex with two Rh-H bonds. For the C=O double bond hydrosilylation, the rate-determining steps of the aCH and DH mechanisms are both acetone insertion into the Rh-H bond, and the order of the activation barrier is DH < aCH ≈ CH < mCH. For the C=C double bond hydrosilylation, except for the mCH pathway whose rate-determining step is the hydrosilane addition reaction, the rate-determining steps of the CH, aCH, and DH pathways are Si-C reductive elimination reactions. The order of the energy barrier is DH ≈ mCH < aCH ≈ CH. In the outer-sphere mechanism, no stable intermediate or transition state was found. Consequently, we concluded that the DH mechanism is adopted as the mechanism for the Rh-catalyzed hydrosilylation of the carbonyl group while the mCH or DH mechanism is adopted as the mechanism for alkenes under conditions where their active intermediates are formed. The present result revises a hypothesis that the hydrosilylation of the carbonyl group is in general accomplished by the mCH mechanism. The active species in the DH mechanism has one more extra Rh-H bond compared to that of the other pathways, and its interaction with a silyl group, trans-influence, and small steric effect are the origin of the highly efficient catalytic activity, which was not reported before.

元の言語英語
ページ(範囲)8552-8561
ページ数10
ジャーナルJournal of Organic Chemistry
84
発行部数13
DOI
出版物ステータス出版済み - 7 5 2019

Fingerprint

Hydrosilylation
Silanes
Rhodium
Calcium Carbonate
Hydrides
Alkenes
Addition reactions
Energy barriers
Acetone
Ketones
Density functional theory
Catalyst activity
Chemical activation

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

これを引用

Theoretical Study on the Rhodium-Catalyzed Hydrosilylation of C=C and C=O Double Bonds with Tertiary Silane. / Zhao, Liming; Nakatani, Naoki; Sunada, Yusuke; Nagashima, Hideo; Hasegawa, Jun Ya.

:: Journal of Organic Chemistry, 巻 84, 番号 13, 05.07.2019, p. 8552-8561.

研究成果: ジャーナルへの寄稿記事

Zhao, Liming ; Nakatani, Naoki ; Sunada, Yusuke ; Nagashima, Hideo ; Hasegawa, Jun Ya. / Theoretical Study on the Rhodium-Catalyzed Hydrosilylation of C=C and C=O Double Bonds with Tertiary Silane. :: Journal of Organic Chemistry. 2019 ; 巻 84, 番号 13. pp. 8552-8561.
@article{948a8251bb6c4fee98e84be444edb081,
title = "Theoretical Study on the Rhodium-Catalyzed Hydrosilylation of C=C and C=O Double Bonds with Tertiary Silane",
abstract = "Reaction mechanisms of hydrosilylation of ketone and alkene with tertiary silane using the Wilkinson-type catalyst were theoretically investigated on the basis of density functional calculations using ωB97XD functional. Previously proposed three mechanisms, the Chalk-Harrod (CH) mechanism, the modified Chalk-Harrod (mCH) mechanism, and the outer-sphere mechanism were examined. Besides, we also found two mechanisms, the alternative CH (aCH) mechanism and the double hydride (DH) mechanism. In the aCH mechanism, a four-coordinate rhodium hydride complex formed through the elimination of R3Si-Cl is a catalytically active species. In the DH mechanism, the active species is a six-coordinate complex with two Rh-H bonds. For the C=O double bond hydrosilylation, the rate-determining steps of the aCH and DH mechanisms are both acetone insertion into the Rh-H bond, and the order of the activation barrier is DH < aCH ≈ CH < mCH. For the C=C double bond hydrosilylation, except for the mCH pathway whose rate-determining step is the hydrosilane addition reaction, the rate-determining steps of the CH, aCH, and DH pathways are Si-C reductive elimination reactions. The order of the energy barrier is DH ≈ mCH < aCH ≈ CH. In the outer-sphere mechanism, no stable intermediate or transition state was found. Consequently, we concluded that the DH mechanism is adopted as the mechanism for the Rh-catalyzed hydrosilylation of the carbonyl group while the mCH or DH mechanism is adopted as the mechanism for alkenes under conditions where their active intermediates are formed. The present result revises a hypothesis that the hydrosilylation of the carbonyl group is in general accomplished by the mCH mechanism. The active species in the DH mechanism has one more extra Rh-H bond compared to that of the other pathways, and its interaction with a silyl group, trans-influence, and small steric effect are the origin of the highly efficient catalytic activity, which was not reported before.",
author = "Liming Zhao and Naoki Nakatani and Yusuke Sunada and Hideo Nagashima and Hasegawa, {Jun Ya}",
year = "2019",
month = "7",
day = "5",
doi = "10.1021/acs.joc.9b00959",
language = "English",
volume = "84",
pages = "8552--8561",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "13",

}

TY - JOUR

T1 - Theoretical Study on the Rhodium-Catalyzed Hydrosilylation of C=C and C=O Double Bonds with Tertiary Silane

AU - Zhao, Liming

AU - Nakatani, Naoki

AU - Sunada, Yusuke

AU - Nagashima, Hideo

AU - Hasegawa, Jun Ya

PY - 2019/7/5

Y1 - 2019/7/5

N2 - Reaction mechanisms of hydrosilylation of ketone and alkene with tertiary silane using the Wilkinson-type catalyst were theoretically investigated on the basis of density functional calculations using ωB97XD functional. Previously proposed three mechanisms, the Chalk-Harrod (CH) mechanism, the modified Chalk-Harrod (mCH) mechanism, and the outer-sphere mechanism were examined. Besides, we also found two mechanisms, the alternative CH (aCH) mechanism and the double hydride (DH) mechanism. In the aCH mechanism, a four-coordinate rhodium hydride complex formed through the elimination of R3Si-Cl is a catalytically active species. In the DH mechanism, the active species is a six-coordinate complex with two Rh-H bonds. For the C=O double bond hydrosilylation, the rate-determining steps of the aCH and DH mechanisms are both acetone insertion into the Rh-H bond, and the order of the activation barrier is DH < aCH ≈ CH < mCH. For the C=C double bond hydrosilylation, except for the mCH pathway whose rate-determining step is the hydrosilane addition reaction, the rate-determining steps of the CH, aCH, and DH pathways are Si-C reductive elimination reactions. The order of the energy barrier is DH ≈ mCH < aCH ≈ CH. In the outer-sphere mechanism, no stable intermediate or transition state was found. Consequently, we concluded that the DH mechanism is adopted as the mechanism for the Rh-catalyzed hydrosilylation of the carbonyl group while the mCH or DH mechanism is adopted as the mechanism for alkenes under conditions where their active intermediates are formed. The present result revises a hypothesis that the hydrosilylation of the carbonyl group is in general accomplished by the mCH mechanism. The active species in the DH mechanism has one more extra Rh-H bond compared to that of the other pathways, and its interaction with a silyl group, trans-influence, and small steric effect are the origin of the highly efficient catalytic activity, which was not reported before.

AB - Reaction mechanisms of hydrosilylation of ketone and alkene with tertiary silane using the Wilkinson-type catalyst were theoretically investigated on the basis of density functional calculations using ωB97XD functional. Previously proposed three mechanisms, the Chalk-Harrod (CH) mechanism, the modified Chalk-Harrod (mCH) mechanism, and the outer-sphere mechanism were examined. Besides, we also found two mechanisms, the alternative CH (aCH) mechanism and the double hydride (DH) mechanism. In the aCH mechanism, a four-coordinate rhodium hydride complex formed through the elimination of R3Si-Cl is a catalytically active species. In the DH mechanism, the active species is a six-coordinate complex with two Rh-H bonds. For the C=O double bond hydrosilylation, the rate-determining steps of the aCH and DH mechanisms are both acetone insertion into the Rh-H bond, and the order of the activation barrier is DH < aCH ≈ CH < mCH. For the C=C double bond hydrosilylation, except for the mCH pathway whose rate-determining step is the hydrosilane addition reaction, the rate-determining steps of the CH, aCH, and DH pathways are Si-C reductive elimination reactions. The order of the energy barrier is DH ≈ mCH < aCH ≈ CH. In the outer-sphere mechanism, no stable intermediate or transition state was found. Consequently, we concluded that the DH mechanism is adopted as the mechanism for the Rh-catalyzed hydrosilylation of the carbonyl group while the mCH or DH mechanism is adopted as the mechanism for alkenes under conditions where their active intermediates are formed. The present result revises a hypothesis that the hydrosilylation of the carbonyl group is in general accomplished by the mCH mechanism. The active species in the DH mechanism has one more extra Rh-H bond compared to that of the other pathways, and its interaction with a silyl group, trans-influence, and small steric effect are the origin of the highly efficient catalytic activity, which was not reported before.

UR - http://www.scopus.com/inward/record.url?scp=85068333590&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85068333590&partnerID=8YFLogxK

U2 - 10.1021/acs.joc.9b00959

DO - 10.1021/acs.joc.9b00959

M3 - Article

C2 - 31189060

AN - SCOPUS:85068333590

VL - 84

SP - 8552

EP - 8561

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 13

ER -