Synthesis of Ti-based multimetallic hydride complexes and dinitrogen activation

2019 Fiscal Year Final Research Report

• Project/Area Number: 17K05823
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Institute of Physical and Chemical Research
• Principal Investigator: Shima Takanori 国立研究開発法人理化学研究所, 開拓研究本部, 専任研究員 (60391976)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Keywords: 窒素分子の活性化 / クロム / ヒドリド錯体 / 水素化

Outline of Final Research Achievements

Activation of dinitrogen (N2) by well-defined metal hydrides is of much interest and importance, but studies in this area have remained limited to date. We report here N2 activation and hydrogenation by C5Me4SiMe3-ligated di- and trinuclear chromium polyhy-dride complexes. Computational studies are also carried out to gain information on the reaction mechanism. Both experimental and computational studies suggest that N2 incorporation into the chromium hydride cluster is involved in the rate-determining step. This work represents the first example of N2 cleavage and hydrogenation by well-defined chromium hydride com-plexes.

Free Research Field

有機金属化学

Academic Significance and Societal Importance of the Research Achievements

構造明確な分子性多金属ヒドリド錯体を用いた窒素分子の活性化は、これまで窒素との親和性が比較的高い4族、5族遷移金属ヒドリド錯体に限られていた。しかし、今回の報告により、初めて6族遷移金属であるクロムヒドリド錯体を用いて窒素分子の活性化に成功した。今後は様々な金属と配位子の組み合わせによる効率的な窒素分子活性化の研究がさらに展開されていくものと期待される。