Powerful Bis-facially Pyrazolate-Bridged Dinuclear Ruthenium Epoxidation Catalyst

Full Text
Powerful-Bis-facially.pdf embargoed access
Request a copy
When filling the form you are requesting a copy of the article, that is deposited in the institutional repository (DUGiDocs), at the autor or main autor of the article. It will be the same author who decides to give a copy of the document to the person who requests it, if it considers it appropriate. In any case, the UdG Library doesn’t take part in this process because it is not authorized to provide restricted articles.
A new bis-facial dinuclear ruthenium complex, {[RuII(bpy)]2(μ-bimp)(μ-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(μ-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−1, 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 ​
​Tots els drets reservats