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Synthesis of Silylyne Platinum Complexes and Their Application to Synergetic Activation of Small Molecules

Research Project

Project/Area Number 24655028
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeSingle-year Grants
Research Field Organic chemistry
Research InstitutionKyoto University

Principal Investigator

TOKITOH Norihiro  京都大学, 化学研究所, 教授 (90197864)

Project Period (FY) 2012-04-01 – 2014-03-31
Project Status Completed (Fiscal Year 2013)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2013: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2012: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywords有機元素化学 / 有機金属化学 / ケイ素 / 白金 / シリレン / シリリン / 分子活性化 / 遷移金属触媒
Research Abstract

Transition metal complexes with multiple bonds between silicon and transition metal atoms have attracted attention because of their unique structures and reactivity. There have been a number of reports on the silicon-metal doubly bonded complexes (silylene complexes), whereas examples of complexes with silicon-transition metal triple bonds (silylyne complexes) are very limited, and thus the properties of silylyne complexes have not been elucidated in detail.
In this study, synthesis of cationic silylyne complexes was investigated by using a bromosilylene complex as the synthetic precursor. However, treatments of the bromosilylene complex with bromide ion abstraction reagents resulted in the decomposition of the starting complex, and the expected cationic silylyne complex could not be observed. We have also synthesized a novel cationic Si(I) species coordinated by Lewis bases, which would be a promising starting material for the cationic silylyne complexes.

Report

(3 results)
  • 2013 Annual Research Report   Final Research Report ( PDF )
  • 2012 Research-status Report
  • Research Products

    (51 results)

All 2014 2013 2012 Other

All Journal Article (13 results) (of which Peer Reviewed: 11 results,  Acknowledgement Compliant: 1 results) Presentation (33 results) (of which Invited: 4 results) Book (4 results) Remarks (1 results)

  • [Journal Article] Syntheses and Structures of Terminal Arylalumylene Complexes2014

    • Author(s)
      長田浩一、吾郷友宏、時任宣博
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 53 Issue: 15 Pages: 3881-3884

    • DOI

      10.1002/anie.201310559

    • NAID

      120005646490

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Unique Synthetic Approach toward a Phosphaalkene : Synthesis of a Selenium-substituted Phosphaalkene with Bulky Substituents2014

    • Author(s)
      K. Sugamata, T. Sasamori, N. Tokitoh
    • Journal Title

      Chem. Lett.

      Volume: 43 Pages: 95-96

    • Related Report
      2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of a Rhodium Carbonyl Phosphaalkenyl–Phosphido Complex : A Phosphorus Congener of Schiff Base Type N,N′-Chelating Monoanionic Ligands2014

    • Author(s)
      Matsumoto, T.; Sasamori, T.; Miyake, H.; Tokitoh, N
    • Journal Title

      Organometallics

      Volume: 33 Issue: 6 Pages: 1341-1344

    • DOI

      10.1021/om500065n

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] 元素化学ひとすじ-分析・解析技術の進歩と共同研究に支えられて2014

    • Author(s)
      時任宣博
    • Journal Title

      化学と工業

      Volume: 71 Pages: 330-340

    • Related Report
      2013 Final Research Report
  • [Journal Article] Synthesis and Structure of a 1-Phospha-2-boraacenaphthene Derivative and Its Chalcogenation Reactions2014

    • Author(s)
      津留崎陽大、笹森貴裕、時任宣博
    • Journal Title

      Chem. Eur. J.

      Volume: 20 Issue: 13 Pages: 3752-3758

    • DOI

      10.1002/chem.201304644

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Unique Synthetic Approach toward a Phosphaalkene: Synthesis of a Selenium-substituted Phosphaalkene with Bulky Substituents2014

    • Author(s)
      菅又功、笹森貴裕、時任宣博
    • Journal Title

      Chem. Lett.

      Volume: 43 Issue: 1 Pages: 95-96

    • DOI

      10.1246/cl.130862

    • NAID

      130004427087

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 1,2-Bis(ferrocenyl)dipnictenes : Bimetallic Systems with a Pn=Pn Heavyπ-Spacer (Pn : P, Sb, and Bi)2013

    • Author(s)
      Sakagami, M.; Sasamori, T.; Sakai, H.; Furukawa, Y.; Tokitoh, N
    • Journal Title

      Bull. Chem. Soc. Jpn

      Volume: 86 Issue: 10 Pages: 1132-1143

    • DOI

      10.1246/bcsj.20130174

    • NAID

      10031201269

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of a Dialumene-Benzene Adduct and Its Reactivity as a Synthetic Equivalent of a Dialumene2013

    • Author(s)
      吾郷友宏, 長田浩一、時任宣博
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 52 Issue: 41 Pages: 10818-10821

    • DOI

      10.1002/anie.201305228

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Structures of an Alumole and its Dianion2013

    • Author(s)
      T. Agou, T. Wasano, P. Jin, S. Nagase, and N. Tokitoh
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 52 Issue: 38 Pages: 10031-10034

    • DOI

      10.1002/anie.201304143

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Step-wise sulfurization of stable 1,2-bis(ferrocenyl)diphosphene2013

    • Author(s)
      笹森貴裕、坂上訓康、時任宣博
    • Journal Title

      J. Sulfur Chem.

      Volume: 34 Issue: 6 Pages: 677-683

    • DOI

      10.1080/17415993.2013.795224

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] 典型元素多重結合の化学における最近の進歩2013

    • Author(s)
      時任宣博
    • Journal Title

      Organometallic News

      Volume: 71 Pages: 61-65

    • Related Report
      2013 Final Research Report
  • [Journal Article] Synthesis of an Arylbromosilylene-Platinum Complex by Using a 1,2-Dibromodisilene as a Silylene Source2012

    • Author(s)
      Agou, T.; Sasamori, T.; Tokitoh, N.
    • Journal Title

      Organometallics

      Volume: 31 Issue: 3 Pages: 1150-1154

    • DOI

      10.1021/om201227p

    • Related Report
      2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Catalytic Activities for Olefin Polymerization : Titanium(III), Titanium(IV), Zirconium(IV), and Hafnium(IV) β-Diketiminato, 1-Aza-1,3-butadienyl-Imido, and 1-Aza-2-butenyl-Imido Complexes Bearing an Extremely Bulky Substituent, the Tbt Group (Tbt=2,4,6-[(Me_3Si)_2CH]_3C_6H_2)2012

    • Author(s)
      Hirofumi Hamaki
    • Journal Title

      Macromolecules

      Volume: 45 Issue: 4 Pages: 1758-1769

    • DOI

      10.1021/ma2024107

    • Related Report
      2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Presentation] かさ高いアリール基を有するアルミレン白金錯体の合成と構造2014

    • Author(s)
      長田浩一,吾郷友宏,時任宣博
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス,名古屋
    • Related Report
      2013 Final Research Report
  • [Presentation] ハロゲン置換アルモールの合成2014

    • Author(s)
      和佐野達也,吾郷友宏,時任宣博
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス,名古屋
    • Related Report
      2013 Final Research Report
  • [Presentation] かさ高い置換基を用いたホスファアルメンの合成検討2014

    • Author(s)
      池田慎,吾郷友宏,時任宣博
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス,名古屋
    • Related Report
      2013 Final Research Report
  • [Presentation] トリホスファ[3]ラジアレンを配位子とする6族遷移金属錯体の合成と構造2014

    • Author(s)
      三宅秀明,笹森貴裕,時任宣博
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス,名古屋
    • Related Report
      2013 Final Research Report
  • [Presentation] 複合的な立体保護基の組み合わせを用いたスタンナベンゼン類の合成とその性質2014

    • Author(s)
      金里脩平,水畑吉行,時任宣博
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス,名古屋
    • Related Report
      2013 Final Research Report
  • [Presentation] 種々の置換様式を有する1,2-ジアルキルジシレン類の合成検討2014

    • Author(s)
      江川泰暢,水畑吉行,時任宣博
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス,名古屋
    • Related Report
      2013 Final Research Report
  • [Presentation] Synthetic Studies on Organoselenium-substituted Phosphenium Cations2014

    • Author(s)
      菅又功,VILLALBA FRANCO, José Manuel,笹森貴裕,時任宣博
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス,名古屋
    • Related Report
      2013 Final Research Report
  • [Presentation] かさ高い置換基を有するセレン置換ホスフェニウムの合成研究2013

    • Author(s)
      菅又功,VILLALBA FRANCO, Jose Manuel,笹森貴裕,時任宣博
    • Organizer
      第40回有機典型元素化学討論会
    • Place of Presentation
      近畿大学,東大阪
    • Related Report
      2013 Final Research Report
  • [Presentation] 安定なアルモール及びそのジアニオンの合成と性質2013

    • Author(s)
      和佐野達也,吾郷友宏,時任宣博
    • Organizer
      第60回有機金属化学討論会
    • Place of Presentation
      学習院大学,東京
    • Related Report
      2013 Final Research Report
  • [Presentation] ジアルメン-ベンゼン付加体の合成と反応 : ジアルメン等価体としての反応性2013

    • Author(s)
      長田浩一,吾郷友宏,時任宣博
    • Organizer
      第24回基礎有機化学討論会
    • Place of Presentation
      学習院大学,東京
    • Related Report
      2013 Final Research Report
  • [Presentation] 4,5,6-Triphospha[3]radialen e : A New Cross-conjugated System2013

    • Author(s)
      N. Tokitoh, H. Miyake, T. Sasamori, J. I.-C. Wu, P. v. R. Schleyer
    • Organizer
      The 15th Asian Chemical Congress
    • Place of Presentation
      Singapore
    • Related Report
      2013 Final Research Report
  • [Presentation] New Approach towards Tellurenyl Cation Species (RTe^+) : Trapping as 2,5-Dihydrotellurophenium Salts and Their Retro Cycloaddition2013

    • Author(s)
      N. Tokitoh, K. Sugamata, T. Sasamori
    • Organizer
      The 12th International Conference on the Chemistry of Selenium and Tellurium (ICCST-12)
    • Place of Presentation
      Cardiff, Wales, UK
    • Related Report
      2013 Final Research Report
    • Invited
  • [Presentation] New Aspects in the Coordination Chemistry of Stannaaromatics2013

    • Author(s)
      N. Tokitoh, Y. Mizuhata, N. Noda
    • Organizer
      14th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (GTL-2013)
    • Place of Presentation
      Nova Scotia, Canada
    • Related Report
      2013 Final Research Report
  • [Presentation] 安定なアルモール及びそのジアニオン種の合成と構造2013

    • Author(s)
      和佐野達也,吾郷友宏,JIN, Peng,永瀬茂,時任宣博
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス,草津
    • Related Report
      2013 Final Research Report
  • [Presentation] 安定なホスファアルメンの合成検討2013

    • Author(s)
      池田慎,吾郷友宏,時任宣博
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス,草津
    • Related Report
      2013 Final Research Report
  • [Presentation] ジアルメン-ベンゼン付加体とアセチレン類との反応2013

    • Author(s)
      長田浩一,吾郷友宏,JIN, Peng,永瀬茂,時任宣博
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス,草津
    • Related Report
      2013 Final Research Report
  • [Presentation] かさ高い立体保護基により安定化したスタンナベンゼン類の合成とその性質2013

    • Author(s)
      金里脩平,水畑吉行,能田直弥,時任宣博
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス,草津
    • Related Report
      2013 Final Research Report
  • [Presentation] 新規なジシレン架橋[2]フェロセノファンの合成研究2013

    • Author(s)
      宮本久,笹森貴裕,時任宣博
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス,草津
    • Related Report
      2013 Final Research Report
  • [Presentation] 安定な1,2-ビス(フェロセニル)ジニクテン類の合成と酸化還元挙動2013

    • Author(s)
      坂上訓康,笹森貴裕,時任宣博
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス,草津
    • Related Report
      2013 Final Research Report
  • [Presentation] かさ高いアミノ置換基を活用した低配位ホウ素化学種の発生研究2013

    • Author(s)
      堤洋介,水畑吉行,時任宣博
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス,草津
    • Related Report
      2013 Final Research Report
  • [Presentation] トリホスファ[3]ラジアレンおよびそのラジカルアニオンの電子密度分布解析2013

    • Author(s)
      三宅秀明,笹森貴裕,時任宣博,橋爪大輔,古川頁,金朋,永瀬茂
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス,草津
    • Related Report
      2013 Final Research Report
  • [Presentation] カルコゲン置換ホスフェニウム類縁体の合成研究2013

    • Author(s)
      菅又功,笹森貴裕,時任宣博
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス,草津
    • Related Report
      2013 Final Research Report
  • [Presentation] New Aspects in the Coordination Chemistry of Stannaaromatics2013

    • Author(s)
      Norihiro Tokitoh, Yoshiyuki Mizuhata, Naoya Noda
    • Organizer
      14th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (GTL 2013)
    • Place of Presentation
      Nova Scotia, Canada
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] New Approach towards Tellurenyl Cation Species (RTe+): Trapping as 2,5-Dihydrotellurophenium Salts and Their Retro Cycloaddition2013

    • Author(s)
      Norihiro Tokitoh, Koh Sugamata, Takahiro Sasamori
    • Organizer
      The 12th International Conference on the Chemistry of Selenium and Tellurium (ICCST-12)
    • Place of Presentation
      Cardiff, Wales, UK
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Triphospha[3]radialene and Its Anionic Species2013

    • Author(s)
      Norihiro Tokitoh
    • Organizer
      The 1st Swiss-Kyoto Symposium, Organic Chemistry and Materials Chemistry
    • Place of Presentation
      ETH Zuerich, Switzerland
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] 安定なアルモール及びそのジアニオン種の合成と構造2013

    • Author(s)
      和佐野達也、吾郷友宏、JIN, Peng、永瀬茂、時任宣博
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス(草津市)
    • Related Report
      2012 Research-status Report
  • [Presentation] 安定なホスファアルメンの合成検討2013

    • Author(s)
      池田慎、吾郷友宏、時任宣博
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス(草津市)
    • Related Report
      2012 Research-status Report
  • [Presentation] かさ高い置換基を有する1,2-ジアリールジアルメンの発生と捕捉2012

    • Author(s)
      長田浩一,吾郷友宏,時任宣博
    • Organizer
      第39回有機典型元素化学討論会
    • Place of Presentation
      いわて県民情報交流センター,盛岡
    • Related Report
      2013 Final Research Report
  • [Presentation] トリホスファ[3]ラジアレンとそのアニオン種の構造2012

    • Author(s)
      三宅秀明,笹森貴裕,時任宣博
    • Organizer
      第23回基礎有機化学討論会
    • Place of Presentation
      京都テルサ,京都
    • Related Report
      2013 Final Research Report
  • [Presentation] 新規なジゲルメン架橋フェロセノファンの発生2012

    • Author(s)
      宮本久,笹森貴裕,時任宣博
    • Organizer
      第59回有機金属化学討論会
    • Place of Presentation
      大阪大学吹田キャンパス,吹田
    • Related Report
      2013 Final Research Report
  • [Presentation] Synthesis and Properties of 1-Phospha-2-boraacenaphthene2012

    • Author(s)
      T. Sasamori, A. Tsurusaki, A. Wakamiya, K. Nagura, S. Irle, S. Yamaguchi, N. Tokitoh
    • Organizer
      The 13th International Symposium on Inorganic Ring Systems
    • Place of Presentation
      Victoria, Canada
    • Related Report
      2013 Final Research Report
  • [Presentation] Synthesis and Properties of Stannabenzenes2012

    • Author(s)
      N. Tokitoh, Y. Mizuhata, N. Noda
    • Organizer
      The 13th International Symposium on Inorganic Ring Systems
    • Place of Presentation
      Victoria, Canada
    • Related Report
      2013 Final Research Report
  • [Presentation] Sulfurization of 1,2-Diaryl-1,2-dibromodisilenes2012

    • Author(s)
      N. Tokitoh, K. Hironaka, Y. Sugiyama, T. Agou, T. Sasamori
    • Organizer
      25th International Symposium on the Organic Chemistry of Sulfur
    • Place of Presentation
      Częstochowa, Poland
    • Related Report
      2013 Final Research Report
  • [Book] "ケイ素-炭素,ケイ素-ヘテロ元素多重結合化合物",現代ケイ素化学,吉良満夫,玉尾皓平編2013

    • Author(s)
      笹森貴裕,時任宣博
    • Publisher
      化学同人
    • Related Report
      2013 Final Research Report
  • [Book] "ケイ素芳香族化合物",現代ケイ素化学,吉良満夫,玉尾皓平編2013

    • Author(s)
      水畑吉行,時任宣博
    • Publisher
      化学同人
    • Related Report
      2013 Final Research Report
  • [Book] "Low-Coordinate Main Group Compounds–Group 14 (Sn, Pb)", Comprehensive Inorganic Chemistry, 2nd Ed., Vol. 1, Ed. By T. Chivers2013

    • Author(s)
      N. Tokitoh, Y. Mizuhata
    • Publisher
      Elsevier
    • Related Report
      2013 Final Research Report
  • [Book] "Low-Coordinate Main Group Compounds-Group 14 (Si, Ge)", Comprehensive Inorganic Chemistry, 2nd Ed., Vol. 12013

    • Author(s)
      N. Tokitoh, T. Sasamori(Ed. by T. Chivers)
    • Publisher
      Elsevier
    • Related Report
      2013 Final Research Report
  • [Remarks] Tokitoh Lab

    • URL

      http://boc.kuicr.kyoto-u.ac.jp/www.

    • Related Report
      2013 Annual Research Report

URL: 

Published: 2013-05-31   Modified: 2019-07-29  

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