Formation of sterically hindered C-C double bonds via catalytic olefin metathesis is considered a very challenging task for Ru catalysts. This limitation led to the development of specialised catalysts bearing sterically reduced N-heterocyclic carbene (NHC) ligands that are very active in such transformations, yet significantly less stable as compared to general purpose catalysts. To decrease the small-size NHC catalysts susceptibility to decomposition, a new NHC ligand was designed, in which two sterically reduced aryl arms were tied together by a C-8 alkyl chain. The installation of this macrocyclic ligand on the ruthenium centre led to the formation of an olefin metathesis catalyst (trans-Ru6). Interestingly, this complex undergoes transformation into an isomer bearing two Cl ligands in the cis-arrangement (cis-Ru6). These two isomeric complexes exhibit similarly high thermodynamic stability, yet different application profiles in catalysis.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC9322543 | PMC |
| http://dx.doi.org/10.1002/anie.202201472 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
An open-shell Ir(II)/Ir(IV) redox couple outperforms an Ir(I)/Ir(III) pair in olefin isomerization.
Nat Chem
January 2025
Instituto de Investigaciones Químicas, Consejo Superior de Investigaciones Científicas and Universidad de Sevilla, Sevilla, Spain.
Open-shell systems based on first-row transition metals and their involvement in various catalytic processes are well explored. By comparison, mononuclear open-shell complexes of precious transition metals remain underdeveloped. This is particularly true for Ir complexes, as there is very limited information available regarding their application in catalysis.
View Article and Find Full Text PDFA Cd-based crystalline network material: catalytic properties and post-synthetic metal-ion metathesis with enhanced stability and gas sorption behaviour.
Dalton Trans
January 2025
Department of Chemistry, Jadavpur University, Jadavpur, Kolkata-700 032, West Bengal, India.
This study presents the synthesis of a Cd(II) based hydrophobic three dimensional crystalline network material (CNM), [Cd(L)(LH)(bpe)], {L = {4,4'-(hexafluroisopropylidine)bis(benzoate)} and 1,2-di(4-pyridyl) ethylene (bpe)}, 1(Cd), by employing the slow-diffusion method. The three-dimensional structure of 1(Cd) was determined by single crystal X-ray diffraction and characterized by powder X-ray diffraction (PXRD), FT-IR spectroscopy and thermogravimetric analysis (TGA). Subsequently, post-synthetic modification of 1(Cd) with Cu(II) at room temperature led to the formation of isostructural 1(Cu) with partial substitution.
View Article and Find Full Text PDFFluorinated Cyclic Olefin Copolymers (COCs) and Cyclic Olefin Polymers (COPs).
Macromol Rapid Commun
January 2025
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Renmin Street 5625, Changchun, 130022, China.
The demand for insulating materials with superior dielectric properties has increased. Among these materials, polymers containing cyclic structure including cyclic olefin copolymer (COC) and cyclic olefin polymer (COP) stand out because of their excellent dielectric properties originating from the pure hydrocarbon structure. Introducing fluorine into polymers is one efficient strategy for optimizing the dielectric and the related important properties.
View Article and Find Full Text PDFArtificial metalloenzyme assembly in cellular compartments for enhanced catalysis.
Nat Chem Biol
January 2025
State Key Laboratory of Chemo/Biosensing and Chemometrics and School of Chemistry and Chemical Engineering, Hunan University, Changsha, China.
Artificial metalloenzymes (ArMs) integrated within whole cells have emerged as promising catalysts; however, their sensitivity to metal centers remains a systematic challenge, resulting in diminished activity and turnover. Here we address this issue by inducing in cellulo liquid-liquid phase separation through a self-labeling fusion protein, HaloTag-SNAPTag. This strategy creates membraneless, isolated liquid condensates within Escherichia coli as protective compartments for the assembly of ArMs using the same fusion protein.
View Article and Find Full Text PDFSynthesis and Reactivity of an Olefin Metathesis-Catalyzing Ruthenium Complex with a Selenoether Moiety in the Benzylidene Ligand.
ACS Omega
December 2024
Division of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan.
A Hoveyda-Grubbs (HG)-type olefin metathesis complex with a selenoether moiety at the terminus of phenoxy moiety was synthesized. The complex showed direct selenium-atom coordination to the ruthenium center, resulting in higher thermodynamic stability compared with the parent HG catalyst. The selenium atom binding enhanced the tolerance to protic solvent molecules in ring-closing metathesis of -tosyldiallylamide and diethyl diallylmalonate, and also in the cross metathesis between 3-butenylbenzoate and methyl acrylate.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!