金属間多重結合錯体のδ型ｄ軌道による感応性発現メカニズムと触媒作用の理論研究

• Project Area: Stimuli-responsive Chemical Species for the Creation of Functional Molecules
• Project/Area Number: 15H00940
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyoto University
• Principal Investigator: 榊 茂好 京都大学, 福井謙一記念研究センター, 研究員 (20094013)
• Project Period (FY): 2015-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥5,980,000 (Direct Cost: ¥4,600,000、Indirect Cost: ¥1,380,000); Fiscal Year 2016: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000); Fiscal Year 2015: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
• Keywords: 遷移金属錯体 / 触媒 / 複合分子 / 金属間結合 / 化学反応 / 小分子活性化 / 理論計算 / ヘテロ元素化合物 / 有機化学 / 理論化学 / 触媒化学プロセス

Outline of Annual Research Achievements

金属多重結合を持つ多核金属錯体の化学は、単核錯体のそれに比べて興味が構造、結合に集中していたため、反応や触媒作用に関する研究が遅れていた。最近、実験分野で触媒反応はそれに直結するσ結合活性化反応が報告されたが、基礎的理解は乏しい。本研究では金属多重結合を持つ２核および３核錯体のＤＦＴおよびCASPT2法による理論的研究を行った。
２核Ｍｏ錯体によるH-H結合の活性化反応について理論的研究を行い、シスジヒドリド中間体を、ほぼ活性障壁無しで生成し、その後、熱的に可能な活性障壁を経由してトランスジヒドリド体を生成することを明らかとし、さらに、この錯体はアルカンのＣ－Ｈ結合やアルコールのＯ－Ｈ結合の活性化にも有効であることを理論的に予測した。これらのσ結合活性化にはＭｏ－Ｍｏ五重結合のδ型ｄ－ｄ結合および反結合軌道が分極しながら関与し、反応を円滑に進めていることが示された。
ＣｒおよびＭｏの３核錯体のCASPT2法による研究では、平成２７年度にＣｒは対称構造を、Ｍｏは非対称構造をとることを明らかにしていたが、２８年度では、Ｃｒの結合次数が形式的な結合次数２に比べ、単結合よりも小さいのは、架橋キレート配位子の配位原子間距離が本来のＣｒ－Ｃｒ結合距離に比べて異常に長いためであることが示された。
これらの多核金属錯体の研究に加え、ピンサー型配位子を持つＰ化合物は通常のＰ化合物と異なり、電子状態が柔軟であることに着目し、その遷移金属錯体類似の触媒反応の理論的研究を行い、反応機構を解明するとともに、新しい二酸化炭素固定化反応にも応用可能なことを理論計算から予測した。

Research Progress Status

28年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

28年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] Beijing University of Chem. Tech./Nanging University(China)
• [Int'l Joint Research] Dr. Harisingh Gour Central University(India)
• [Journal Article] Theoretical Study of Nickel-Catalyzed Selective Alkenylation of Pyridine: Reaction Mecha- nism and Crucial Roles of Lewis Acid and Ligands in Determining the Selectivity (2017)
  • Author(s): Vijay Singh, Yoshiaki Nakao, Shigeyoshi Sakaki*, and Milind M. Deshmukh
  • Journal Title: J. Org. Chem. Volume: 82 Issue: 1 Pages: 289-301
  • DOI: 10.1021/acs.joc.6b02394
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] 3D-RISM-MP2 Approach to Hydration Structure of Pt(II) and Pd(II) Complexes: Unusual H-Ahead Mode vs Usual O-Ahead One (2016)
  • Author(s): S. Aono, T. Mori, S. Sakaki
  • Journal Title: Journal of Chemical Theory and Computation Volume: 12 Issue: 3 Pages: 1189-1206
  • DOI: 10.1021/acs.jctc.5b01137
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Stabilization of a Silaaldehyde by its η2-Coordination to Tungsten (2016)
  • Author(s): Tetsuya Fukuda, Hisako Hashimoto, Shigeyoshi Sakaki, Hiromi Tobita
  • Journal Title: Angewandte Chemie International Edition Volume: 55 Issue: 1 Pages: 188-192
  • DOI: 10.1002/anie.201507956
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Theoretical Study of Hydrogenation Catalysis of Phosphorus Compound and Prediction of Catalyst with High Activity and Wide Application Scope (2016)
  • Author(s): Zeng, G.; Maeda, S.; Taketsugu, T.; Sakaki, S.
  • Journal Title: ACS Cat. Volume: 6 Issue: 8 Pages: 4859-4870
  • DOI: 10.1021/acscatal.5b02968
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Catalytic Hydrogenation of Carbon Dioxide with Ammonia-Borane by Pincer-Type Phosphorus Compounds: Theoretical Prediction (2016)
  • Author(s): Zeng, GX.; Maeda, S.; Taketsugu, T.; Sakaki, S.
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Issue: 41 Pages: 13481-13484
  • DOI: 10.1021/jacs.6b07274
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Reasons Two Nonstrained C-C σ-Bonds Can Be Easily Cleaved in Decyanative [4+2] Cy-cloaddition Catalyzed by Nickel(0)/Lewis Acid Systems. Theoretical Insight (2015)
  • Author(s): Wei Guan, Shigeyoshi Sakaki, Takuya Kurahashi, and Seijiro Matsubara
  • Journal Title: ACS Cat Volume: 5 Issue: 1 Pages: 1-10
  • DOI: 10.1021/cs501653s
  • Peer Reviewed
• [Journal Article] Theoretical and Computational Study of a Complex System Consisting of Transition Metal Element(s): How to Understand and Predict Its Geometry, Bonding Nature, Molecular Property, and Reaction Behavior (2015)
  • Author(s): Shigeyoshi Sakaki
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 88 Issue: 7 Pages: 889-938
  • DOI: 10.1246/bcsj.20150119
  • NAID: 130005088018
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Activation of Strong Boron－Fluorine and Silicon－Fluorine sigma-Bonds: Theoretical Understanding and Prediction (2015)
  • Author(s): Hajime Kameo, Shigeyoshi Sakaki
  • Journal Title: Chemistry - A European Journal Volume: 21 Issue: 39 Pages: 13588-13597
  • DOI: 10.1002/chem.201502197
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] How Can We Understand Au8 Cores and Entangled Ligands of Selenolate- and Thiolate-Protected Gold Nanoclusters Au24(ER)20 and Au20(ER)16 (E = Se, S; R = Ph, Me)? A Theoretical Study (2015)
  • Author(s): Nozomi Takagi,Kazuya Ishimura, Masafuyu Matsui, Ryoichi Fukuda, Toru Matsui, Takahito Nakajima, Masahiro Ehara, and Shigeyoshi Sakaki
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 26 Pages: 8593-8602
  • DOI: 10.1021/jacs.5b04337
  • Peer Reviewed
• [Journal Article] Heterolytic Activation of Dihydrogen Molecule by Hydroxo-/Sulfido-Bridged Rutheni um-Germanium Dinuclear Complex. Theoretical Insights (2014)
  • Author(s): N. Ochi, T. Matsumoto, T. Dei, Y. Nakao, H. Sato, K. Tatsumi, S. Sakaki
  • Journal Title: Inorg. Chem. Volume: 54 Issue: 2 Pages: 576-585
  • DOI: 10.1021/ic502463y
  • Peer Reviewed
• [Journal Article] Isolation of a Hydrogen-Bridged Bis(silylene) Tungsten Complex : A Snapshot of a Transition State for 1, 3-Hydrogen Migration (2014)
  • Author(s): Hisako Hashimoto, Yuto Odagiri, Yasuhiro Yamada, Nozomi Takagi, Shigeyoshi Sakaki, and Hiromi Tobita
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 1 Pages: 158-161
  • DOI: 10.1021/ja512336v
  • Peer Reviewed / Open Access
• [Presentation] Crucial Role of Lewis Acid in Enhancing Reactivity of Organometallic Complex (2016)
  • Author(s): Shigeyoshi Sakaki
  • Organizer: The 1’st International Conference for Organometallic Chemistry
  • Place of Presentation: Beijing
  • Year and Date: 2016-10-23
  • Int'l Joint Research / Invited
• [Presentation] QM/MM 法による金(I)-イソシアニド錯体の吸収・発光に対する結晶効果の研究 (2016)
  • Author(s): 青野真冶、榊 茂好
  • Organizer: 第10回分子科学討論会
  • Place of Presentation: 神戸
  • Year and Date: 2016-09-13
• [Presentation] 静電ポテンシャルを考慮したembedded cluster modelの構築 (2016)
  • Author(s): 松井正冬、榊 茂好
  • Organizer: 第10回分子科学討論会
  • Place of Presentation: 福岡
  • Year and Date: 2016-09-13
• [Presentation] Effects of molecular crystal on absorption and emission spectra of gold(I)-isocyanide complex: Theoretical study with QM/MM approach (2016)
  • Author(s): Shinji Aono and Shigeyosh Sakaki
  • Organizer: 錯体化学会第66回討論会
  • Place of Presentation: 福岡
  • Year and Date: 2016-09-10
• [Presentation] Theoretical investigation of trinuclear Cr(II) complex: Characteristic features of bridged metal-metal multiple bonds (2016)
  • Author(s): Masayuki Nakagaki and Shigeyoshi Sakaki
  • Organizer: 錯体化学会第66回討論会
  • Place of Presentation: 福岡
  • Year and Date: 2016-09-10
• [Presentation] Complex Systems Consisting of Transition Metal and Heavy Main Group Elements: Theoretical Study of Structure and Bonding Nature (2016)
  • Author(s): Shigeyoshi Sakaki
  • Organizer: The 70th Fujihara Seminar “New Development of PhysicalOrganic Chemistry: Construction of Chemical Principles Determining Structures, Reactions, and Properties.
  • Place of Presentation: Fukuoka
  • Year and Date: 2016-04-18
  • Int'l Joint Research / Invited
• [Presentation] Theoretical Study of Complex System Consisting of Transition Metal Element(s) (2016)
  • Author(s): Shigeyoshi Sakaki
  • Organizer: The Seven-th Asia-Pacific Confernece on Theoretical and Computational Chemistry
  • Place of Presentation: Kaoshiung, Taiwan
  • Year and Date: 2016-01-25
  • Int'l Joint Research / Invited
• [Presentation] 触媒の理論化学 /計算化学研究：元素戦略的触媒開発へ貢献を目指して (2016)
  • Author(s): 榊 茂好
  • Organizer: 第四回元素戦略に基づいた触媒設計シンポジウム
  • Place of Presentation: 東京
  • Invited
• [Presentation] Theoretical understanding of catalysis by transition metal complex with unusual valence (2015)
  • Author(s): Shigeyoshi Sakaki
  • Organizer: Pacifichem2015
  • Place of Presentation: Honolulu, Hawai, U. S. A.
  • Year and Date: 2015-12-15
  • Int'l Joint Research / Invited
• [Presentation] Catalysis of Main Group Element Compound in Comparison with Transition Metal Complex from the Viewpoint of Theoretical Study (2015)
  • Author(s): Shigeyoshi Sakaki
  • Organizer: ICIQ-FIFC Spain-Japan Joint Symposium on Complex Systems
  • Place of Presentation: Tarragona, Spain
  • Year and Date: 2015-11-25
  • Int'l Joint Research / Invited
• [Presentation] 遷移金属元素とケイ素化学種の相互作用と反応過程の理論研究: 面白さと難しさ (2015)
  • Author(s): 榊 茂好
  • Organizer: 第１９回ケイ素化学シンポジウム
  • Place of Presentation: 琵琶湖ラフォーレ
  • Year and Date: 2015-10-23
  • Invited
• [Presentation] Bonding Nature, Reactivity and Catalysis of M-M Multiple Bond: Theoretical Study (2015)
  • Author(s): Yue Chen, Masayuki Nakagaki, Shigeyoshi Sakaki
  • Organizer: The 6th JCS(Japan-Czech-Slovakia)-Joint Symposium
  • Place of Presentation: Somlenice, Slovakia
  • Year and Date: 2015-10-11
  • Int'l Joint Research / Invited
• [Remarks]
  • URL: http://www.sakakigroup.fukui.kyoto-u.ac.jp/
• [Remarks] 榊グループ
  • URL: http://www.sakakigroup.fukui.kyoto-u.ac.jp/