具有相邻反应位点的异双核Ru-Co配合物对烯烃氢化协同催化作用的机理洞察

Mechanistic Insight into Synergistic Catalysis of Olefin Hydrogenation by a Hetero-Dinuclear Ru-Co Complex with Adjacent Reaction Sites.

作者信息

Hong Dachao, Ohgomori Yuji, Shimoyama Yoshihiro, Kotani Hiroaki, Ishizuka Tomoya, Kon Yoshihiro, Kojima Takahiko

机构信息

Interdisciplinary Research Center for Catalytic Chemistry , National Institute of Advanced Industrial Science and Technology (AIST) , 1-1-1 Higashi , Tsukuba , Ibaraki 305-8565 , Japan.

Department of Chemistry, Faculty of Pure and Applied Sciences , University of Tsukuba, CREST, Japan Science and Technology Agency (JST) , 1-1-1 Tennoudai , Tsukuba , Ibaraki 305-8571 , Japan.

出版信息

Inorg Chem. 2019 Sep 3;58(17):11284-11288. doi: 10.1021/acs.inorgchem.9b02104. Epub 2019 Aug 9.

DOI:10.1021/acs.inorgchem.9b02104

PMID:31398017

Abstract

We have designed and synthesized a hetero-dinuclear Ru-Co complex with a dinucleating ligand inspired by hetero-dinuclear active sites of metalloenzymes. A synergistic effect between the adjacent Ru and Co sites has been confirmed in catalytic olefin hydrogenation by the complex, exhibiting a much higher turnover number than those of mononuclear Ru or Co complexes as the components. A Ru-hydrido species was detected by H NMR and electrospray ionization (ESI)-time-of-flight (TOF)-MS measurements as an intermediate to react with olefins, and Co-bound methanol was suggested to act as a proton source.

摘要

我们设计并合成了一种具有双核配体的异双核钌-钴配合物，其灵感来源于金属酶的异双核活性位点。该配合物在催化烯烃加氢反应中，相邻的钌和钴位点之间存在协同效应，与作为组分的单核钌或钴配合物相比，其周转数要高得多。通过核磁共振氢谱（H NMR）和电喷雾电离（ESI）-飞行时间（TOF）-质谱测量检测到一种钌氢化物物种作为与烯烃反应的中间体，并推测与钴结合的甲醇充当质子源。