Powerful Bis-facially Pyrazolate-Bridged Dinuclear Ruthenium Epoxidation Catalyst
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- 作者：Joan Aguil贸 ; Laia Franc脿s ; Roger Bofill ; Marcos Gil-Sepulcre ; Jordi Garc铆a-Ant贸n ; Albert Poater ; Antoni Llobet ; Llu铆s Escriche ; Franc Meyer ; Xavier Sala
- 刊名：Inorganic Chemistry
- 出版年：2015
- 出版时间：July 20, 2015
- 年：2015
- 卷：54
- 期：14
- 页码：6782-6791
- 全文大小：527K
- ISSN：1520-510X
文摘
A new bis-facial dinuclear ruthenium complex, {[RuII(bpy)]2(渭-bimp)(渭-Cl)}2+, 22+, containing a hexadentate pyrazolate-bridging ligand (Hbimp) and bpy as auxiliary ligands has been synthesized and fully characterized in solution by spectrometric, spectroscopic, and electrochemical techniques. The new compound has been tested with regard to its capacity to oxidize water and alkenes. The in situ generated bis-aqua complex, {[RuII(bpy)(H2O)]2(渭-bimp)}3+, 33+, is an excellent catalyst for the epoxidation of a wide range of alkenes. High turnover numbers (TN), up to 1900, and turnover frequencies (TOF), up to 73 min鈥?, are achieved using PhIO as oxidant. Moreover, 33+ presents an outstanding stereospecificity for both cis and trans olefins toward the formation of their corresponding epoxides due to specific interactions transmitted by its ligand scaffold. A mechanistic analysis of the epoxidation process has been performed based on density functional theory (DFT) calculations in order to better understand the putative cooperative effects within this dinuclear catalyst.