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Conversion of Dinitrogen to Organo-Nitrogen Compounds by Multimetallic Hydride Complexes

Research Project

Project/Area Number 26410082
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionInstitute of Physical and Chemical Research

Principal Investigator

SHIMA Takanori  国立研究開発法人理化学研究所, 侯有機金属化学研究室, 専任研究員 (60391976)

Project Period (FY) 2014-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2016: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2014: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords窒素分子活性化 / チタンヒドリド錯体 / ニトリド錯体 / ニトリル / 酸塩化物 / 窒素活性化 / 含窒素有機化合物 / チタン錯体 / ヒドリド錯体
Outline of Final Research Achievements

At present, ammonia, produced by the Haber-Bosch process, is the only nitrogen source for the industrial preparation of nitrogen-containing organic products. Although the activation and functionalization of N2 under milder conditions have received much recent interest, studies on the direct use of N2 as a feedstock for organic synthesis are still in their infancy.
We have found that the titanium diimide/dinitride complex, formed by activation of N2 with H2 and the titanium trialkyl complex, served as a unique platform for the synthesis of nitriles through reaction with acid chlorides. This protocol features simple reaction condition, no requirement for extra reagents, and unprecedented functional group tolerance. 15N-Isotope labeled nitriles can also be efficiently prepared by using the 15N-enriched diimide/dinitride analogue derived from 15N2 gas. The titanium complexes could be recycled by treatment of the crude reaction mixture with HCl.

Report

(4 results)
  • 2016 Annual Research Report   Final Research Report ( PDF )
  • 2015 Research-status Report
  • 2014 Research-status Report
  • Research Products

    (32 results)

All 2017 2016 2015 2014 Other

All Journal Article (9 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 8 results,  Acknowledgement Compliant: 5 results) Presentation (18 results) (of which Int'l Joint Research: 3 results,  Invited: 3 results) Book (3 results) Remarks (1 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Dinitrogen Activation by Dihydrogen and a PNP-Ligated Titanium Complex2017

    • Author(s)
      B. Wang, G. Luo, M. Nishiura, S. Hu, T. Shima, Y. Luo, and Z. Hou
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 139 Issue: 5 Pages: 1818-1821

    • DOI

      10.1021/jacs.6b13323

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Cleavage of Carbon Monoxide and C-C Bond Formation Promoted by Rare-Earth/Ruthenium Heterobimetallic Hydride Complexes2017

    • Author(s)
      D. Kawai, T. Shima, M. Nishiura, Z. Hou
    • Journal Title

      J. Organomet. Chem.

      Volume: 印刷中 Pages: 74-81

    • DOI

      10.1016/j.jorganchem.2017.02.042

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Conversion of Dinitrogen to Nitriles at a Multinuclear Titanium Framework2016

    • Author(s)
      M. M. Guru, T. Shima, and Z. Hou
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 55 Issue: 40 Pages: 12316-12320

    • DOI

      10.1002/anie.201607426

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Gyroscope-Like Complexes Based on Dibridgehead Diphosphine Cages That Are Accessed by Three-Fold Intramolecular Ring Closing Metatheses and Encase Fe(CO)3, Fe(CO)2(NO)+, and Fe(CO)3(H)+ Rotators2016

    • Author(s)
      Georgette M. Lang, Takanori Shima, Leyong Wang, Kyle J. Cluff, Katrin Skopek, Frank Hampel, Janet Bluemel, John A. Gladysz
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 138 Issue: 24 Pages: 7649-7663

    • DOI

      10.1021/jacs.6b03178

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 多核チタンヒドリド錯体による窒素分子の切断と水素化2016

    • Author(s)
      島 隆則、侯 召民
    • Journal Title

      ファインケミカル

      Volume: 3月号 Pages: 27-32

    • Related Report
      2015 Research-status Report
  • [Journal Article] Rare-Earth/Iridium Heterobimetallic Complexes with Bridging Imido and Silylmethyl Ligands: Synthesis, Structure and Reactivity2015

    • Author(s)
      Takanori Shima, Takako Yanagi, Zhaomin Hou
    • Journal Title

      New Journal of Chemistry

      Volume: 39 Issue: 10 Pages: 7608-7616

    • DOI

      10.1039/c5nj00598a

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Syntheses of Iron(0) Complexes of Symmetrical Trialkylphosphines with Three Terminal Vinyl Groups, P((CH2)mCH=CH2)32015

    • Author(s)
      Georgette M. Lang, Dirk Skaper, Takanori Shima, Michael Otto, Leyong Wang, John A. Gladysz
    • Journal Title

      Australian Journal of Chemistry

      Volume: 68 Pages: 1342-1351

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Journal Article] Carbon-carbon bond cleavage and rearrangement of benzene by a trinuclear titanium hydride2014

    • Author(s)
      S. Hu, T. Shima, Z. Hou
    • Journal Title

      Nature

      Volume: 512 Issue: 7515 Pages: 413-415

    • DOI

      10.1038/nature13624

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Trinuclear μ3-Silyl Complexes of Ruthenium and Group 9 Metals Having 3c-2e Interactions and Transformation of a μ3-Silyl Complex of Ru2Ir into μ-Silyl and μ3-Silylene Complexes2014

    • Author(s)
      Masahiro Nagaoka, Takanori Shima, Toshiro Takao, Hiroharu, Suzuki
    • Journal Title

      Organometallics

      Volume: 33 Issue: 24 Pages: 7232-7240

    • DOI

      10.1021/om5010308

    • Related Report
      2014 Research-status Report
    • Peer Reviewed
  • [Presentation] 多核チタンヒドリド錯体による窒素分子変換反応の開発2017

    • Author(s)
      島 隆則
    • Organizer
      第97回日本化学会春季年会特別企画
    • Place of Presentation
      慶應義塾大学(神奈川県横浜市)
    • Year and Date
      2017-03-19
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] 多核チタンヒドリド錯体による窒素分子の活性化2016

    • Author(s)
      島 隆則
    • Organizer
      理研シンポジウム「第17回 分析・解析技術と化学の最先端」
    • Place of Presentation
      理化学研究所(埼玉県和光市)
    • Year and Date
      2016-12-16
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] Conversion of Dinitrogen to Nitriles by Titanium Complexes2016

    • Author(s)
      Takanori Shima
    • Organizer
      The 1st Japan-Australia Joint Symposium on Coordination Chemistry
    • Place of Presentation
      福岡大学(福岡県福岡市)
    • Year and Date
      2016-09-10
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 多金属チタンヒドリド錯体による窒素分子の活性化と含窒素有機化合物の合成2016

    • Author(s)
      島 隆則
    • Organizer
      第5回JACI/GSCシンポジウム
    • Place of Presentation
      ANAクラウンプラザホテル神戸(兵庫県神戸市)
    • Year and Date
      2016-06-02
    • Related Report
      2016 Annual Research Report
  • [Presentation] 様々なCp基を有するハーフサンドイッチ型チタン錯体による窒素分子の活性化2016

    • Author(s)
      島 隆則、胡 少偉、侯 召民
    • Organizer
      第96回日本化学会春季年会
    • Place of Presentation
      京田辺、同志社大学
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Denitrogenation of Pyridine Derivatives Mediated by a Titanium Hydride Complex2016

    • Author(s)
      Shoawei Hu, Gen Luo, Takanori Shima, Yi Luo, Zhaomin Hou
    • Organizer
      第96回日本化学会春季年会
    • Place of Presentation
      京田辺、同志社大学
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Dinitrogen activation by multinuclear titanium polyhydride complexes2015

    • Author(s)
      Takanori Shima, Shaowei Hu, Gen Luo, Xiaohui Kang, Yi Luo, Zhaomin Hou
    • Organizer
      PACIFICHEM2015
    • Place of Presentation
      Hilton Hawaiian Village, Hawaii
    • Year and Date
      2015-12-19
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Carbon-carbon bond cleavage and rearrangement of benzene by a multinuclear titanium hydride complex2015

    • Author(s)
      Shaowei Hu, Takanori Shima, Xiaohui Kang, Gen Luo, Yi Luo, Zhaomin Hou
    • Organizer
      PACIFICHEM2015
    • Place of Presentation
      Hilton Hawaiian Village, Hawaii
    • Year and Date
      2015-12-17
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Chemistry of Multimetallic Polyhydride Clusters: Activation and Transformation of Dinitrogen and Benzene2015

    • Author(s)
      Takanori Shima
    • Organizer
      第65回錯体化学討論会
    • Place of Presentation
      奈良、奈良女子大学
    • Year and Date
      2015-09-21
    • Related Report
      2015 Research-status Report
  • [Presentation] 多金属チタンヒドリド錯体による窒素分子の活性化と含窒素有機化合物の合成2015

    • Author(s)
      島 隆則・Murali Mohan Guru・羅 根・胡 少偉・羅 一・侯 召民
    • Organizer
      第62回有機金属化学討論会
    • Place of Presentation
      大阪、関西大学
    • Year and Date
      2015-09-09
    • Related Report
      2015 Research-status Report
  • [Presentation] 多金属チタンヒドリド錯体を用いた窒素分子の活性化2015

    • Author(s)
      島 隆則
    • Organizer
      第48回有機金属若手の会夏の学校
    • Place of Presentation
      滋賀、白浜荘
    • Year and Date
      2015-07-13
    • Related Report
      2015 Research-status Report
  • [Presentation] Denitrogenation of pyridine by a trinuclear titanium polyhydride complex2015

    • Author(s)
      Shaowei Hu, Gen Luo, Takanori Shima, Yi Luo, Zhaomin Hou
    • Organizer
      第95回日本化学会春季年会
    • Place of Presentation
      船橋、日本大学
    • Year and Date
      2015-03-28
    • Related Report
      2014 Research-status Report
  • [Presentation] Synthesis of nitrogen-containing organic compounds by dinitrogen activation with multimetallic titanium polyhydrides2015

    • Author(s)
      Murali Mohan Guru, Takanori Shima, Zhaomin Hou
    • Organizer
      第95回日本化学会春季年会
    • Place of Presentation
      船橋、日本大学
    • Year and Date
      2015-03-28
    • Related Report
      2014 Research-status Report
  • [Presentation] Chemistry of multimetallic polyhydride complexes: Activation and transformation of N2 and benzene2015

    • Author(s)
      Takanori Shima
    • Organizer
      The 1st CSRS-ITbM Joint Workshop
    • Place of Presentation
      名古屋、名古屋大学
    • Year and Date
      2015-01-07
    • Related Report
      2014 Research-status Report
  • [Presentation] 多金属チタンヒドリド錯体を用いたベンゼンの炭素―炭素結合切断と骨格変換反応2014

    • Author(s)
      胡 少偉・島 隆則・亢 小輝・羅 一・羅 根・侯 召民
    • Organizer
      第61回有機金属化学討論会
    • Place of Presentation
      福岡、九州大学
    • Year and Date
      2014-09-24
    • Related Report
      2014 Research-status Report
  • [Presentation] 窒素分子活性化による四核チタンイミド/ニトリド錯体の合成と水素化反応2014

    • Author(s)
      島 隆則・羅 根・胡 少偉・遠藤 慶徳・羅 一・侯 召民
    • Organizer
      錯体化学会第64回討論会
    • Place of Presentation
      東京、中央大学
    • Year and Date
      2014-09-18
    • Related Report
      2014 Research-status Report
  • [Presentation] 多核チタンヒドリド錯体による窒素分子の活性化と触媒的アンモニア合成への展開2014

    • Author(s)
      遠藤 慶徳・島 隆則・侯 召民
    • Organizer
      錯体化学会第64回討論会
    • Place of Presentation
      東京、中央大学
    • Year and Date
      2014-09-18
    • Related Report
      2014 Research-status Report
  • [Presentation] Dinitrogen Cleavage and Hydrogenation by Multinuclear Titanium Polyhydride Complexes2014

    • Author(s)
      Takanori SHIMA, Shaowei HU, Gen LUO, Xiaohui KANG, Yi LUO, and Zhaomin HOU
    • Organizer
      The 26th International Conference on Organometallic Chemistry (ICOMC 2014)
    • Place of Presentation
      Sapporo, Royton Sapporo Hotel
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Research-status Report
  • [Book] Dinitrogen fixation by transition metal hydride complexes2017

    • Author(s)
      Takanori Shima, Zhaomin Hou
    • Publisher
      Springer
    • Related Report
      2016 Annual Research Report
  • [Book] Molecular rare earth hydride clusters2016

    • Author(s)
      Takanori Shima, Zhaomin Hou
    • Publisher
      Springer
    • Related Report
      2015 Research-status Report
  • [Book] 水素利用技術集成vol.42014

    • Author(s)
      島隆則、侯召民ほか
    • Total Pages
      332
    • Publisher
      エヌ・ティー・エス
    • Related Report
      2014 Research-status Report
  • [Remarks] 侯有機金属化学研究室

    • URL

      http://www.riken.jp/lab-www/organometallic/index.html

    • Related Report
      2016 Annual Research Report 2015 Research-status Report 2014 Research-status Report
  • [Patent(Industrial Property Rights)] 金属錯体、及び、金属錯体を用いた含窒素有機化合物の合成法2015

    • Inventor(s)
      侯召民・島隆則・グルムラリモハン
    • Industrial Property Rights Holder
      侯召民・島隆則・グルムラリモハン
    • Industrial Property Rights Type
      特許
    • Filing Date
      2015-03-05
    • Related Report
      2014 Research-status Report

URL: 

Published: 2014-04-04   Modified: 2018-03-22  

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