Chiral Molecular Metal Chains

• Project Area: Coordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
• Project/Area Number: 17H05374
• 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: Nara Women's University
• Principal Investigator: 棚瀬 知明 奈良女子大学, 自然科学系, 教授 (50207156)
• Project Period (FY): 2017-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000); Fiscal Year 2018: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000); Fiscal Year 2017: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
• Keywords: 分子性金属鎖 / 不斉 / パラジウム / 多座ホスフィン / 分子デバイス / 光学分割

Outline of Annual Research Achievements

本研究では，申請者のPd8核鎖を中心とするこれまでの研究を基盤に，キラルな直鎖状四座ホスフィンrac-dpmppmに支持されたPd4核鎖を構造単位とし，電解還元を用いた逐次的伸長法により低原子価分子性金属ワイヤーの創成を行う。Pd8核鎖生成過程で見出されたPd4核ユニット間のキラル識別を介した自発的な自己整列のメカニズムを精査し金属鎖の拡張に応用する。また，不斉な置換基を導入したキラルな直鎖状四座ホスフィンを新たに設計し，それらを用いてキラルな分子性金属鎖の合成を行い，得られたPdを中心とする分子性金属鎖の不斉に由来する物性・反応性等を明らかにし，それらキラル物性を利用した新たな機能の開発を目的とする。本年度は，１）キラルな直鎖状四座ホスフィンrac-dpmppmを用いたパラジウム分子ワイヤーの合成と自己不斉認識によるPd鎖の拡張として，rac-dpmppmをHPLCキラルカラムにより光学分割し，キラルなPd８核鎖 [Pd8(R,R-dpmppm)4(CH3CN)2](BF4)4 及び[Pd8(S,S-dpmppm)4(CH3CN)2](BF4)4 を合成し単離することに成功した。また，２）新奇不斉四座ホスフィン配位子によるキラルな分子性金属鎖の創成として，N原子で連結された直鎖状四座ホスフィン（dpmppaR, R = Ph）を合成し，ホモキラルなdpmppaPhにより支持された直鎖状Pd４核鎖の合成に成功し，さらに，一連のPd/Pt混合金属４核鎖（PtPd3, PtPd2Pt, Pt2Pd2, Pt2PdPt）を構築することで一次元合金金属鎖というこれまでにない新たな概念の分子素子を提案するに至った（Chem. Eur. J. 2019, inside cover pictureに採択された）。

Research Progress Status

平成30年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

平成30年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] N-Acyclic carbene complexes supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) as an asymmetric pincer ligand (2019)
  • Author(s): Tanase Tomoaki、Urabe Mari、Mori Natsumi、Hatada Satoko、Noda Sayo、Takenaka Hiroe、Nakamae Kanako、Nakajima Takayuki
  • Journal Title: Journal of Organometallic Chemistry Volume: 879 Pages: 47-59
  • DOI: 10.1016/j.jorganchem.2018.10.005
  • Peer Reviewed
• [Journal Article] A decanuclear Pt complex comprised of an unbridged Pt4 chain capped by two Pt3 A-frame units supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (2019)
  • Author(s): Tanase Tomoaki、Urabe Mari、Takenaka Hiroe、Nakamae Kanako、Nakajima Takayuki
  • Journal Title: Journal of Organometallic Chemistry Volume: 883 Pages: 41-46
  • DOI: 10.1016/j.jorganchem.2019.01.010
  • Peer Reviewed
• [Journal Article] Synthesis and characterization of iridium hydride complexes with meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) as an unsymmetric pincer ligand (2019)
  • Author(s): Tanase Tomoaki、Mori Natsumi、Nakamae Kanako、Nakajima Takayuki
  • Journal Title: Journal of Organometallic Chemistry Volume: 888 Pages: 54-64
  • DOI: 10.1016/j.jorganchem.2019.03.010
  • Peer Reviewed
• [Journal Article] Alloyed Tetranuclear Metal Chains of Pd4-nPtn (n = 0-3) Scaffolded by a New Linear Tetraphosphine Containing a PNP Bridge (2019)
  • Author(s): T. Tanase*, M. Tanaka, M. Hamada, Y. Morita, K. Nakamae, Y. Ura,. T. Nakajima*
  • Journal Title: Chem. Eur. J. Volume: 25
  • Peer Reviewed
• [Journal Article] 直鎖状多座ホスフィンにより構造規制された遷移金属クラスター ―分子性金属鎖の化学を中心に― (2019)
  • Author(s): 棚瀬 知明
  • Journal Title: Organometallic News (近畿化学協会) Volume: 1 Pages: 14-19
  • Peer Reviewed
• [Journal Article] Tri- and Tetranuclear Copper Hydride Complexes Supported by Tetradentate Phosphine Ligands (2018)
  • Author(s): Nakajima Takayuki、Kamiryo Yoshia、Hachiken Kanae、Nakamae Kanako、Ura Yasuyuki、Tanase Tomoaki
  • Journal Title: Inorganic Chemistry Volume: 57 Issue: 17 Pages: 11005-11018
  • DOI: 10.1021/acs.inorgchem.8b01628
  • Peer Reviewed
• [Journal Article] Chiral Self-Recognition between Stereogenic Tetrapalladium Units Affording Pd8 Chains Supported by Homochiral Tetraphosphines (2017)
  • Author(s): T. Tanase, K. Morita, R. Otaki, K. Yamamoto, Y. Kaneko, K. Nakamae, B. Kure, and T. Nakajima
  • Journal Title: Chem. Eur. J. Volume: 23 Pages: 524-528
  • Peer Reviewed
• [Journal Article] Planar PtPd3 Complexes Stabilized by Three Bridging Silylene Ligands (2017)
  • Author(s): M. Tanabe, R. Yumoto, T. Yamada, T. Fukuta, T. Hoshino, K. Osakada, and T. Tanase
  • Journal Title: Chem. Eur. J. Volume: 23 Pages: 1386-1392
  • Peer Reviewed
• [Journal Article] Linear Triplatinum Tetrahydride Complex Supported by Triphosphine Ligands, [Pt3(mu-H)2(H)2(mu-dpmp)2](BF4)2 {dpmp = bis(diphenylphosphinomethyl)phenylphosphine} (2017)
  • Author(s): T. Tanase, K. Yamamoto, R. Hatano, K. Nakamae, B. Kure, Y. Ura, and T. Nakajima
  • Journal Title: Eur. J. Inorg. Chem. Volume: no Pages: 1422-1426
  • Peer Reviewed
• [Journal Article] A Fluxional Cu8H6 Cluster Supported by Bis(diphenylphosphino)methane and Its Facile Reaction with CO2 (2017)
  • Author(s): K. Nakamae, M. Tanaka, B. Kure, T. Nakajima, Y. Ura, and T. Tanase
  • Journal Title: Chem. Eur. J. Volume: 23 Pages: 9457-9461
  • Peer Reviewed
• [Journal Article] Synthesis and Reactivity of Thiolate-bridged NiIIMI Heterodinuclear Complexes (M = Rh, Ir) with an S-Bidentate NiP2S2 Metalloligand (2017)
  • Author(s): B. Kure, M. Sano, N. Watanabe, T. Nakajima, and T. Tanase
  • Journal Title: Eur. J. Inorg. Chem. Volume: no Pages: 4097-4109
  • Peer Reviewed
• [Presentation] 直鎖状多座ホスフィンにより構造規制された遷移金属クラスター ―分子性金属鎖の化学を中心に― (2018)
  • Author(s): 棚瀬 知明
  • Organizer: 平成30年度近畿化学協会有機金属部会例会
  • Invited
• [Presentation] Multinuclear Metal Centers Constrained by Linear Polyphosphines, Focusing on Metal Atom Chains (2018)
  • Author(s): T. Tanase
  • Organizer: 43rd International Conference on Coordination Chemistry
  • Int'l Joint Research / Invited
• [Presentation] 直鎖状多座ホスフィンにより構造規制された遷移金属クラスター ―分子性金属鎖の化学を中心に― (2017)
  • Author(s): 棚瀬知明
  • Organizer: 第50回有機金属若手の会夏の学校
  • Invited
• [Presentation] Multinuclear Metal Centers Constrained by Linear Polyphosphines (2017)
  • Author(s): Tomoaki Tanase
  • Organizer: 11th Japan-China Joint Symposium on Metal Cluster Compounds
  • Int'l Joint Research / Invited
• [Presentation] Self-Alignment of Low-Valent Palladium Chains with meso/rac-tetraphosphine, Self-Chiral Recognition of Pd4 Units (2017)
  • Author(s): Tomoaki Tanase
  • Organizer: 4th Japan-Canada Joint Symposium on Coordination Chemistry
  • Int'l Joint Research / Invited
• [Presentation] Self-Alignment of Low-Valent Palladium Chains with meso/rac-tetraphosphine, Self-Chiral Recognition of Pd4 Units (2017)
  • Author(s): Tomoaki Tanase
  • Organizer: 4th Japan-Taiwan-Singapore-Hong Kong Quadrilateral Symposium on Coordination Chemistry
  • Int'l Joint Research / Invited
• [Remarks] Tanase Research Group Home Page
  • URL: http://www.chem.nara-wu.ac.jp/~tanase/TanaseGroup/
• [Remarks] Tanase Group Home Page
  • URL: http://www.chem.nara-wu.ac.jp/~tanase/TanaseGroup/