Synthesis of Ti-based multimetallic hydride complexes and dinitrogen activation

• Project/Area Number: 17K05823
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Institute of Physical and Chemical Research
• Principal Investigator: Shima Takanori 国立研究開発法人理化学研究所, 開拓研究本部, 専任研究員 (60391976)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2018: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: 窒素分子の活性化 / クロム / ヒドリド錯体 / 水素化 / 窒素分子活性化 / イミド錯体 / アミド錯体 / クロムヒドリド錯体 / ニトリド錯体 / アルキンカップリング / チタン錯体 / ヒドリド / 窒素分子

Outline of Final Research Achievements

Activation of dinitrogen (N2) by well-defined metal hydrides is of much interest and importance, but studies in this area have remained limited to date. We report here N2 activation and hydrogenation by C5Me4SiMe3-ligated di- and trinuclear chromium polyhy-dride complexes. Computational studies are also carried out to gain information on the reaction mechanism. Both experimental and computational studies suggest that N2 incorporation into the chromium hydride cluster is involved in the rate-determining step. This work represents the first example of N2 cleavage and hydrogenation by well-defined chromium hydride com-plexes.

Academic Significance and Societal Importance of the Research Achievements

構造明確な分子性多金属ヒドリド錯体を用いた窒素分子の活性化は、これまで窒素との親和性が比較的高い4族、5族遷移金属ヒドリド錯体に限られていた。しかし、今回の報告により、初めて6族遷移金属であるクロムヒドリド錯体を用いて窒素分子の活性化に成功した。今後は様々な金属と配位子の組み合わせによる効率的な窒素分子活性化の研究がさらに展開されていくものと期待される。

Research Products

• [Int'l Joint Research] 大連理工大(中国)
• [Int'l Joint Research] 大連理工大(中国)
• [Journal Article] Dinitrogen Activation and Hydrogenation by C5Me4SiMe3-Ligated Di- and Trinuclear Chromium Hydride Complexes (2020)
  • Author(s): Shima Takanori、Yang Jimin、Luo Gen、Luo Yi、Hou Zhaomin
  • Journal Title: Journal of the American Chemical Society Volume: 142 Issue: 19 Pages: 9007-9016
  • DOI: 10.1021/jacs.0c02939
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Synthesis and diverse transformations of a dinitrogen dititanium hydride complex bearing rigid acridane-based PNP-pincer ligands. (2020)
  • Author(s): Mo, Z.; Shima, T.; Hou, Z.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 59 Issue: 22 Pages: 8635-8644
  • DOI: 10.1002/anie.201916171
  • Peer Reviewed
• [Journal Article] Dinitrogen Activation by a Titanium/Ruthenium Heteromultimetallic Hydride Complex (2020)
  • Author(s): Shima Takanori、Hou Zhaomin
  • Journal Title: European Journal of Inorganic Chemistry Volume: 2020 Issue: 15-16 Pages: 1418-1422
  • DOI: 10.1002/ejic.201901290
  • Peer Reviewed
• [Journal Article] Multimetallic Rare Earth and Group 4 Transition Metal Hydrides for Novel Transformations of Small Molecules (2020)
  • Author(s): Shima Takanori
  • Journal Title: Journal of the Physical Society of Japan Volume: 89 Issue: 5 Pages: 051014-051014
  • DOI: 10.7566/jpsj.89.051014
  • NAID: 210000158050
  • Peer Reviewed
• [Journal Article] 多金属ヒドリド錯体による窒素分子および含窒素有機化合物の変換反応 (2019)
  • Author(s): 島隆則、侯召民
  • Journal Title: 触媒 Volume: 61 Pages: 285-290
  • NAID: 40022047271
• [Journal Article] Experimental and Computational Studies of Dinitrogen Activation and Hydrogenation at a Tetranuclear Titanium Imide/Hydride Framework (2019)
  • Author(s): T. Shima, G. Luo, S. Hu, Y. Luo, Z. Hou
  • Journal Title: J. Am. Chem. Soc. Volume: 141 Issue: 6 Pages: 2713-2720
  • DOI: 10.1021/jacs.8b13341
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Hydrodenitrogenation of pyridines and quinolines at a multinuclear titanium hydride framework (2017)
  • Author(s): Hu Shaowei、Luo Gen、Shima Takanori、Luo Yi、Hou Zhaomin
  • Journal Title: Nature Communications Volume: 8 Issue: 1 Pages: 1-8
  • DOI: 10.1038/s41467-017-01607-z
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Partially Shielded Fe(CO)3 Rotors: Syntheses, Structures, and Dynamic Properties of Complexes with Doubly trans Spanning Diphosphines, trans-Fe(CO)3(PhP((CH2)n)2PPh) (2017)
  • Author(s): Steigleder Esther、Shima Takanori、Lang Georgette M.、Ehnbom Andreas、Hampel Frank、Gladysz John A.
  • Journal Title: Organometallics Volume: 36 Issue: 15 Pages: 2891-2901
  • DOI: 10.1021/acs.organomet.7b00330
  • Peer Reviewed
• [Presentation] Dinitrogen Activation by Molecular Multimetallic Titanium Polyhydrides (2020)
  • Author(s): Takanori Shima, Zhaomin Hou
  • Organizer: International Symposium Hydrogenomics (Sapporo, Japan)
  • Int'l Joint Research
• [Presentation] 窒素分子活性化による三核クロムイミド錯体の合成と水素化反応 (2020)
  • Author(s): 島 隆則、侯 召民
  • Organizer: 第100回日本化学会春季年会（千葉、東京理科大学）
• [Presentation] Dinitrogen Activation by a Trinuclear Chromium Hydride Complex (2019)
  • Author(s): Takanori Shima, Jinmin Yang, Gen Luo, Yi Luo, Zhaomin Hou
  • Organizer: 錯体化学会第69回討論会（名古屋、名古屋大学）
• [Presentation] Multinuclear hydride clusters: Activation and transformation of small molecules (2019)
  • Author(s): Takanori Shima
  • Organizer: The 5th Japan-Korea Joint Symposium on Hydrogen in Materials (Tokyo Tech)
  • Int'l Joint Research
• [Presentation] 多金属ヒドリドによる新規物質変換反応 (2019)
  • Author(s): 島 隆則
  • Organizer: 第13回物性科学領域横断研究会（東京、東大）
• [Presentation] 多金属ヒドリドクラスターによる小分子の活性化と物質変換反応の開発 (2019)
  • Author(s): 島 隆則
  • Organizer: 第99回日本化学会春季年会アドバンストテクノロジープログラム（神戸、甲南大学）
  • Invited
• [Presentation] Dinitrogen Activation by Multinuclear Chromium Hydride Complexes (2018)
  • Author(s): T. Shima, G. Luo, S. Hu, Y. Luo, Z. Hou
  • Organizer: International Conference on Coordination Chemistry (Sendai, Japan)
  • Int'l Joint Research
• [Presentation] 多金属ヒドリドクラスターによる新規反応プロセスの開拓 (2018)
  • Author(s): 島 隆則
  • Organizer: 第1回ハイドロジェノミクス研究会
  • Invited
• [Presentation] チタンヒドリドクラスターを用いた窒素分子の活性化 (2018)
  • Author(s): 島 隆則
  • Organizer: 第12回物性科学領域横断研究会（奈良、奈良先端大）
• [Presentation] Molecular Multimetallic Polyhydrides: Activation and Functionalization of Dinitrogen and Aromatics (2018)
  • Author(s): Takanori Shima
  • Organizer: I2CNER International Workshops 2018 (Kyusyu Univ.)
  • Int'l Joint Research / Invited
• [Presentation] 二核クロムヒドリド錯体の合成と窒素分子の活性化 (2018)
  • Author(s): 島 隆則、侯 召民
  • Organizer: 日本化学会 第98春季年会（船橋、日本大学）
• [Presentation] C-H and C-N bonds cleavage of substituted pyridines by a trinuclear Ti hydride complex (2018)
  • Author(s): Shaowei Hu, Takanori Shima, Zhaomin Hou
  • Organizer: 日本化学会 第98春季年会（船橋、日本大学）
• [Presentation] Hydrodeoxygenative C-C Coupling and Deoxygenative Nitrogenation/Trimerization of Aromatic Aldehydes by a N2-Derived-Imide Hydride Tetranuclear Titanium Complex (2017)
  • Author(s): Yat-Ming So, Takanori Shima, Murali Mohan Guru, Zhaomin Hou
  • Organizer: 第67回錯体化学会討論会（北海道、北海道大学）
• [Presentation] Hydrodenitrogenation of Pyridines and Quinolines at a Multinuclear Titanium Hydride Framework (2017)
  • Author(s): Shaowei Hu, Gen Luo, Takanori Shima, Yi Luo, Zhaomin Hou
  • Organizer: 第67回錯体化学会討論会（北海道、北海道大学）
• [Book] 錯体化合物事典 (2019)
  • Author(s): 錯体化学会
  • Total Pages: 1000
  • Publisher: 朝倉書店
  • ISBN: 9784254141054
• [Remarks] 理研研究室ホームページ
  • URL: http://www2.riken.jp/lab-www/organometallic/index.html
• [Remarks] Researchmap
  • URL: https://researchmap.jp/takanori_shima/
• [Remarks] ORCID
  • URL: https://orcid.org/0000-0003-1813-0439
• [Remarks] 島隆則(ホームページ)
  • URL: https://takanori0606.wixsite.com/mysite
• [Remarks] ResearcherID
  • URL: https://publons.com/researcher/2149634/takanori-shima/
• [Remarks] 理化学研究所侯有機金属化学研究室ホームページ
  • URL: http://www2.riken.jp/lab-www/organometallic/index.html
• [Remarks] 侯有機金属化学研究室
  • URL: http://www.riken.jp/lab-www/organometallic/index.html