Development of New Catalysts Based on Half-Sandwich Metal Complex Structures

2018 Fiscal Year Final Research Report

• Project/Area Number: 26220802
• Research Category: Grant-in-Aid for Scientific Research (S)
• Allocation Type: Single-year Grants
• Research Field: Inorganic chemistry
• Research Institution: Institute of Physical and Chemical Research
• Principal Investigator: Hou Zhaomin 国立研究開発法人理化学研究所, 開拓研究本部, 主任研究員 (10261158)
• Project Period (FY): 2014-05-30 – 2019-03-31
• Keywords: 希土類 / チタン / ヒドリドクラスター / シクロペンタジエニル基 / C-H結合活性化 / 不斉触媒 / 自己修復材料 / 非極性と極性オレフィンとの共重合

Outline of Final Research Achievements

This project aimed to develop new catalysts, new reactions and new functional materials superior or complementary to the existing ones. By using half-sandwich rare-earth catalysts, we have achieved for the first time the copolymerization of ethylene and polar alpha-olefins in a controlled fashion, which afforded new functional polyolefins with excellent self-healing and shape-memory properties. We have synthesized a series of chiral half-sandwich rare-earth alkyl complexes that show excellent enantioselectivity and activity in various transformations such as asymmetric C-H, N-H and Si-H alkylation via C=C insertion. By using molecular metal hydride clusters, we have achieved the activation and transformation of inactive small molecules and aromatic skeletons under mild conditions such as conversion of N2 to nitriles and hydrodenitrogenation of pyridine. This work has not only opened up new avenues in chemical science, but may also offer new entries into chemical industry innovation.

Free Research Field

有機金属化学　触媒化学　有機合成化学　高分子化学

Academic Significance and Societal Importance of the Research Achievements

本研究の成果は、有機金属化学や触媒化学、有機合成化学、高分子合成化学などの基礎科学分野の新しいフロンティアの開拓のみならず、新たな知財の形成や新産業の創出にもつながることが期待できる。例えば、本研究を通して創製された新規自己修復ポリマーは、空気中だけでなく、水や酸、アルカリ性水溶液中でも優れた自己修復性能や形状記憶性能を示し、従来のものでは見られない実用性の高い新機能性材料として多方面から大きな期待が寄せられている。