Development of FLP-type acid/base catalysts using PNP-pincer type phosphaalkene complexes as a Lewis acid

• Project/Area Number: 17K14485
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Synthetic chemistry
• Research Institution: National Institute of Advanced Industrial Science and Technology (2018-2019); Kyoto University (2017)
• Principal Investigator: Takeuchi Katsuhiko 国立研究開発法人産業技術総合研究所, 材料・化学領域, 研究員 (90724097)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000); Fiscal Year 2019: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2018: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2017: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: ホスファアルケン / FLP / ピンサー型錯体 / 二酸化炭素 / ルイス酸 / カチオン性錯体 / Eind基 / 遷移金属錯体 / 白金錯体 / Gutmann–Beckett法 / Rind基 / 有機金属化学

Outline of Final Research Achievements

In this study, we tried the development of FLP using the metal complex of the PNP pincer-type phosphaalkene ligand (BPEP), which improve the Lewis acidity of the coordinated metal, and their application to catalytic reactions.
As a result, we have developed the Eind2-BPEP, which has bulky and ring-fused Eind groups as a steric protection group. Then, we found that the cationic Cu(I) complex with the Eind2-BPEP ligand with a Hünig’s base acts as FLPs and activate hydrogen and phenylacetylene, catalyzes the hydrogenation and hydrosilylation of CO2.

Academic Significance and Societal Importance of the Research Achievements

本研究は、PNPピンサー型ホスファアルケン配位子という高いπ受容性と柔軟な電子構造を有する特色ある配位子に着目し、これに嵩高いEind基を導入することで、これまで困難とされてきた後期遷移金属錯体をルイス酸としたFLPの構築とその触媒反応への応用を実現した。さらに、後期遷移金属のソフトなルイス酸性と挿入反応を利用した新規化学変換プロセスによって、典型元素化合物を用いたFLPでは困難であったCO2の水素化を達成し、基礎分野および応用分野の両面で学術的に意義のある成果となった。

Research Products

• [Journal Article] Cu(I) complex bearing a PNP-pincer-type phosphaalkene ligand with a bulky fused-ring Eind group: properties and applications to FLP-type bond activation and catalytic CO2 reduction (2020)
  • Author(s): Takeuchi Katsuhiko、Tanaka Yuto、Tanigawa Ippei、Ozawa Fumiyuki、Choi Jun-Chul
  • Journal Title: Dalton Transactions Volume: 49 Issue: 11 Pages: 3630-3637
  • DOI: 10.1039/d0dt00276c
  • Peer Reviewed
• [Journal Article] On the Geometrical Stability of Square‐Planar Platinum(0) Complexes That Bear a PNP‐Pincer‐Type Phosphaalkene Ligand (Eind 2 ‐BPEP) (2018)
  • Author(s): Taguchi Hiro‐omi、Tanigawa Ippei、Takeuchi Katsuhiko、Ozawa Fumiyuki
  • Journal Title: Chemistry - A European Journal Volume: 24 Issue: 64 Pages: 17055-17061
  • DOI: 10.1002/chem.201803097
  • Peer Reviewed
• [Journal Article] Frustrated Lewis Pairの基礎と最新動向 (2018)
  • Author(s): 竹内勝彦
  • Journal Title: ペトロテック = Petrotech : 石油学会情報誌 Volume: 41 Pages: 953-957
  • NAID: 40021755629
  • Peer Reviewed
• [Presentation] PNP ピンサー型ホスファアルケン配位子を有するカチオン性銅錯体の合成と CO2 のヒドロシリル化及び水素化触媒への応用 (2017)
  • Author(s): 田中裕人・竹内勝彦・小澤文幸
  • Organizer: 第21回ケイ素化学協会シンポジウム