Highly efficient catalysts for the activation of inert substrates with the assist of synergetic interaction between base metal and metalloid

• Project/Area Number: 15K21222
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Inorganic chemistry; Synthetic chemistry
• Research Institution: Kyushu University
• Principal Investigator: Tahara Atsushi 九州大学, 先導物質化学研究所, 助教 (50713145)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2016: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000); Fiscal Year 2015: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: 鉄 / ケイ素 / アルケンの水素化 / コバルト / 理論計算 / アルケンのヒドロシリル化 / 計算科学 / σ-CAM / 貴金属代替反応 / 金属-配位子の協同作用 / ホウ素 / 水素化 / 貴金属代替

Outline of Final Research Achievements

The purpose of the research is to replace noble-metal-catalysts for the reduction of unsaturated bonds into base-metal-catalysts. Iron complex 1, which bears Fe-Si bonds, catalyzed hydrogenation of alkenes under mild condition (1 atm of H2 at ambient temperature). Theoretical studies revealed that H-H bond is activated not on the iron center but with the assist of Fe-Si bond to afford Fe-H and Si-H bond with lower energy barrier. This system could be applied into other metals by synthesizing Ru analogues. Finally, we achieved to develop highly efficient Fe catalysts for the hydrogenation of sterically-hindered tetrasubstituted alkenes.

Research Products

• [Journal Article] Disilaruthena- and Ferracyclic Complexes Containing Isocyanide Ligands as Effective Catalysts for Hydrogenation of Unfunctionalized Sterically Hindered Alkenes (2018)
  • Author(s): Sunada, Y.; Ogushi, H.; Yamamoto, T.; Uto, S.; Sawano, M.; Tahara, A.; Tanaka, H.; Shiota, Y.; Yoshizawa, K.; Nagashima, H.
  • Journal Title: Journal of the American Chemical Society Volume: 140 Issue: 11 Pages: 4119-4134
  • DOI: 10.1021/jacs.8b00812
  • Peer Reviewed
• [Journal Article] σ-CAM Mechanisms for the Hydrogenation of Alkenes by cis- and trans-Disilametallacyclic Carbonyl Complexes (M = Fe, Ru, Os): Experimental and Theoretical Studies (2017)
  • Author(s): K. Miyamoto, A. Tahara, Y. Sunada, H. Tutumi, R. Inoue, H. Tanaka, Y. Shiota, K. Yoshizawa, and H. Nagashima
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 99 Issue: 5 Pages: 613-626
  • DOI: 10.1246/bcsj.20170004
  • NAID: 130006770718
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] ベースメタルと典型元素による分子活性化の最近の動向 (2017)
  • Author(s): 田原 淳士
  • Journal Title: Organometallic News Volume: 2 Pages: 80-80
  • Peer Reviewed
• [Journal Article] Catalyst Design of Iron Complexes (2017)
  • Author(s): Hideo Nagashima
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 90 Issue: 7 Pages: 761-775
  • DOI: 10.1246/bcsj.20170071
  • NAID: 130005773710
  • Peer Reviewed / Open Access
• [Journal Article] Disilametallacyclic chemistry for efficient catalysis (2017)
  • Author(s): Sunada, Y.; Nagashima, H.
  • Journal Title: Dalton Transaction Volume: 46 Issue: 24 Pages: 7644-7655
  • DOI: 10.1039/c7dt01275f
  • Peer Reviewed
• [Journal Article] Theoretical Study of the Catalytic Hydrogenation of Alkenes by a Disilaferracyclic Complex: Can the Fe-Si s-Bond-assisted Activation of H-H Bonds Allow Development of an Efficient Catalysis of Iron? (2016)
  • Author(s): A. Tahara, H. Tanaka, Y. Sunada, Y. Shiota, K. Yoshizawa, and H. Nagashima
  • Journal Title: J. Org. Chem. Volume: 81 Issue: 22 Pages: 10900-10911
  • DOI: 10.1021/acs.joc.6b01961
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] アルケンのヒドロシリル化用鉄・コバルト触媒の開発 (2016)
  • Author(s): 永島 英夫, 真川 敦嗣, 田原 淳士, 砂田 祐輔,作田 晃司, 野田 大輔
  • Journal Title: ケイ素化学協会誌 Volume: 第33号 Pages: 4-13
  • Peer Reviewed
• [Journal Article] Non-Precious-Metal Catalytic Systems Involving Iron or Cobalt Carboxylates and Alkyl Isocyanides for Hydrosilylation of Alkenes with Hydrosiloxanes (2016)
  • Author(s): Daisuke Noda, Atsushi Tahara, Yusuke Sunada, Hideo Nagashima,
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Issue: 8 Pages: 2480-2483
  • DOI: 10.1021/jacs.5b11311
  • Peer Reviewed
• [Journal Article] Catalyst Design of Vaska-Type Iridium Complexes for Highly Efficient Synthesis of π-Conjugated Enamines (2015)
  • Author(s): Atsushi Tahara, Yasumitsu Miyamoto, Ryota Aoto, Keisuke Shigeta, Yuta Une, Yusuke Sunada, Hideo Nagashima,
  • Journal Title: Organometallics Volume: 34 Issue: 20 Pages: 4985-4907
  • DOI: 10.1021/acs.organomet.5b00636
  • Peer Reviewed
• [Presentation] Theoretical Studies of the Catalytic Hydrogenation of Alkenes by a series of Disilametallacyclic iron and ruthenium Complexes (2017)
  • Author(s): 田原淳士・田中宏昌・砂田祐輔・塩田淑仁・吉澤一成・永島英夫
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応大学日吉キャンパス、神奈川
  • Year and Date: 2017-03-16
• [Presentation] Exploration of iridium catalysts which achieves highly efficient hydrosilane reduction of carbonyl compounds (2017)
  • Author(s): 宇根悠太、田原淳士、永島英夫
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応大学日吉キャンパス、神奈川
  • Year and Date: 2017-03-16
• [Presentation] Synthesis and Characterization of Donnor-Acceptor Compounds Having π-Conjugated Enamines by Iridium-catalyzed Selective Hydrosilane Reduction of Carboxamides (2017)
  • Author(s): 北原いくみ、永島英夫、田原淳士
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応大学日吉キャンパス、神奈川
  • Year and Date: 2017-03-16
• [Presentation] A Theoretical Study of the Catalytic Hydrogenation of Alkenes by Disilaruthenacyclic Complexes (2017)
  • Author(s): 星香花、田原淳士、田中宏昌、砂田祐輔、塩田淑仁、吉澤一成、永島英夫
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応大学日吉キャンパス、神奈川
  • Year and Date: 2017-03-16
• [Presentation] ジシラメタラサイクル骨格を有する8族遷移金属錯体を用いたアルケンの水素化に関する理論研究 (2017)
  • Author(s): 田原 淳士
  • Organizer: 統合物質創成科学研究推進機構 (IRCCS) 第1回若手研究者の会
  • Invited
• [Presentation] Theoretical Studies of the Hydrogenation of Alkenes catalyzed by a Series of Disilametallacyclic Complexes which bears cis- or trans-Dicarbonyl Ligands (M = Fe, Ru, Os) (2017)
  • Author(s): 田原淳士、砂田祐輔、田中宏昌、塩田淑仁、吉澤一成、永島英夫
  • Organizer: 第64回有機金属化学討論会
• [Presentation] 8族遷移金属錯体を用いた他置換アルケンの水素化に関する理論研究 (2017)
  • Author(s): 田原淳士、永島英夫
  • Organizer: 統合物質創製化学研究推進機構 第3回国内シンポジウム
• [Presentation] Theoretical Studies of the Catalytic Hydrogenation of Alkenes by Disilametallacyclic Complexes bearing cis- and trans-Dicarbonyl Ligands (M = Fe, Ru, Os) (2017)
  • Author(s): Atsushi Tahara, Yusuke Sunada, Hiromasa Tanaka, Yoshihito Shiota, Kazunari Yoshizawa, Hideo Nagashima
  • Organizer: the 19th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 19)
  • Int'l Joint Research
• [Presentation] Theoretical Studies of the Catalytic Hydrogenation of Alkenes by Disilametallacyclic Complexes bearing cis- and trans-Dicarbonyl Ligands (M = Fe, Ru, Os) (2017)
  • Author(s): Atsushi Tahara, Konoka Hoshi, Yusuke Sunada, Hiromasa Tanaka, Yoshihito Shiota, Kazunari Yoshizawa, Hideo Nagashima,
  • Organizer: IRCCS-JST CREST Joint Symposium
  • Int'l Joint Research
• [Presentation] CATALYST DESIGN OF VASKA-TYPE IRIDIUM COMPLEXES FOR HIGHLY EFFICIENT SYNTHESIS OF π-CONJUGATED ENAMINES FROM CARBOXAMIDES (2017)
  • Author(s): Atsushi TAHARA, Yasumitsu MIYAMOTO, Keisuke SHIGETA, Yuta UNE, Yusuke SUNADA, Hideo NAGASHIMA
  • Organizer: IMCE 2017
  • Place of Presentation: Kyushu University, Fukuoka
  • Int'l Joint Research
• [Presentation] ジシラルテナサイクル骨格を有するルテニウムビスイソシアニド錯体を用いた多置換アルケンの触媒的水素化反応に関する理論研究 (2016)
  • Author(s): 田原淳士・砂田祐輔・田中宏昌・吉澤一成・永島英夫
  • Organizer: 第20回ケイ素化学協会シンポジウム
  • Place of Presentation: 安芸グランドホテル、広島
  • Year and Date: 2016-10-07
• [Presentation] シラルテナサイクル骨格を有するルテニウムビスカルボニル錯体を用いたアルケンの触媒的水素化反応に関する理論研究 (2016)
  • Author(s): 星香花・田原淳士・砂田祐輔・田中宏昌・吉澤一成・永島英夫
  • Organizer: 第20回ケイ素化学協会シンポジウム
  • Place of Presentation: 安芸グランドホテル、広島
  • Year and Date: 2016-10-07
• [Presentation] 鉄及びコバルトカルボン酸塩とイソシアニド配位子を用いたアルケンのヒドロシリル化触媒の開発 (2016)
  • Author(s): 野田大輔・田原淳士・砂田祐輔・永島英夫
  • Organizer: 第63回有機金属化学討論会
  • Place of Presentation: 早稲田大学西早稲田キャンパス、東京
  • Year and Date: 2016-09-14
• [Presentation] 溶媒によって安定化された単核鉄触媒を用いた原子移動ラジカル重合反応 (2016)
  • Author(s): 中西崇一朗・田原淳士・河村充展・砂田祐輔・永島英夫
  • Organizer: 第63回有機金属化学討論会
  • Place of Presentation: 早稲田大学西早稲田キャンパス、東京
  • Year and Date: 2016-09-14
• [Presentation] A Theoretical Study of the Hydrogenation of Alkenes catalyzed by Iron Complexes bearing Disilametallacycle Moieties (2016)
  • Author(s): Atsushi Tahara
  • Organizer: BASE METAL CATALYSIS SYMPOSIUM
  • Place of Presentation: Princeton University, USA
  • Year and Date: 2016-09-01
  • Int'l Joint Research / Invited
• [Presentation] 8族遷移金属触媒を用いた還元反応に関する計算科学的考察 (2016)
  • Author(s): 田原 淳士
  • Organizer: 統合物質創製化学研究推進機構キックオフシンポジウム
  • Place of Presentation: 名古屋大学、愛知
  • Year and Date: 2016-06-22
• [Presentation] New Iron and Ruthenium Catalysts for Hydrogenation of Alkenes (2016)
  • Author(s): Yusuke Sunada, Atsushi Tahara and Hideo Nagashima
  • Organizer: THE 70th FUJIHARA Seminar
  • Place of Presentation: THE LUIGANS, Fukuoka
  • Year and Date: 2016-04-17
  • Int'l Joint Research / Invited
• [Presentation] 鉄触媒を用いるケイ素材料製造プロセスの最先端 (2016)
  • Author(s): 永島英夫
  • Organizer: 第96回日本化学会春季年会
  • Place of Presentation: 同支社大学
  • Year and Date: 2016-03-24
  • Invited
• [Presentation] イリジウム触媒を用いるアミドのヒドロシラン還元による共役系エナミンの合成：基質および触媒の構造が反応性に及ぼす影響 (2016)
  • Author(s): 田原淳士, 宇根悠太, 宮本保光, 重田啓介, 砂田祐輔, 永島英夫
  • Organizer: 第96回日本化学会春季年会
  • Place of Presentation: 同志社大学
  • Year and Date: 2016-03-24
• [Presentation] Mechanistic Study for Alkene Hydrogenation catalyzed by Ruthenium Complexes bearing Disilametallacycle Moieties (2016)
  • Author(s): 田原 淳士, 田中宏昌, 砂田祐輔, 吉澤一成, 永島英夫
  • Organizer: The 5th International Conference on the MEXT Project of Integrated Research on Chemical Synthesis "Chemical Science for Future Societies"
  • Place of Presentation: 名古屋大学
  • Year and Date: 2016-01-29
  • Int'l Joint Research
• [Presentation] A Theoretical Study of the Catalytic Hydrogenation of Alkenes by Disilametallacyclic Complexes (2016)
  • Author(s): Atsushi Tahara
  • Organizer: JST-NTU Joint Seminar on Sustainable Synthesis and Catalysis
  • Place of Presentation: Nanyang Technological University, Singapore
  • Int'l Joint Research / Invited
• [Presentation] Catalyst design of Vaska-type iridium complexes for efficient synthesis of π-conjugated enamines. (2015)
  • Author(s): Atsushi Tahara, Yusuke Sunada, Yukihiro Motoyama, Hideo Nagashima
  • Organizer: PACIFICHEM2015
  • Place of Presentation: Hilton Hawaiian Village
  • Year and Date: 2015-12-14
  • Int'l Joint Research
• [Presentation] Hydrosilylation of alkenes by common metal catalyst systems. (2015)
  • Author(s): Hideo Nagashima, Daisuke Noda, Yusuke Sunada, Atsushi Tahara
  • Organizer: PACIFICHEM2015
  • Place of Presentation: Hilton Hawaiian Village
  • Year and Date: 2015-12-14
  • Int'l Joint Research / Invited
• [Presentation] ジシラメタラサイクル骨格を有する鉄触媒を用いたアルケンの水素化に関する反応機構研究 (2015)
  • Author(s): 田原 淳士, 田中宏昌, 砂田祐輔, 吉澤一成, 永島英夫
  • Organizer: 第62回有機金属化学討論会
  • Place of Presentation: 関西大学
  • Year and Date: 2015-09-07
• [Remarks] 鉄が生み出す新たな可能性
  • URL: https://news.mynavi.jp/article/nanotech2018-9/
• [Remarks] http://nagashima-lab.cm.kyushu-u.ac.jp/
• [Patent(Industrial Property Rights)] エナミン化合物およびその用途 (2017)
  • Inventor(s): 永島英夫、田原淳士、北原いくみ
  • Industrial Property Rights Holder: 永島英夫、田原淳士、北原いくみ
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2017-039057
  • Filing Date: 2017-03-02
• [Patent(Industrial Property Rights)] ヒドロシリル化反応触媒 (2015)
  • Inventor(s): 永島英夫, 砂田祐輔, 田原淳士, 野田大輔, 作田晃司
  • Industrial Property Rights Holder: 永島英夫, 砂田祐輔, 田原淳士, 野田大輔, 作田晃司
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2015-140722
  • Filing Date: 2015-07-14
• [Patent(Industrial Property Rights)] ヒドロシリル化反応触媒 (2015)
  • Inventor(s): 永島英夫,砂田祐輔,田原淳士,野田大輔,副島廣恵,作田晃司
  • Industrial Property Rights Holder: 永島英夫,砂田祐輔,田原淳士,野田大輔,副島廣恵,作田晃司
  • Industrial Property Rights Type: 特許
  • Filing Date: 2015-08-12
  • Overseas
• [Patent(Industrial Property Rights)] ヒドロシリル化反応触媒 (2015)
  • Inventor(s): 永島英夫,砂田祐輔,田原淳士,野田大輔,副島廣恵,作田晃司
  • Industrial Property Rights Holder: 永島英夫,砂田祐輔,田原淳士,野田大輔,副島廣恵,作田晃司
  • Industrial Property Rights Type: 特許
  • Filing Date: 2015-08-12
  • Overseas