A series of [Ru(Cp/Cp*)(PN)(MeCN)]PF complexes were prepared, in which the steric and electronic properties of the primary coordination sphere were varied (R = Ph, t-Bu, Bn; and Cp vs. Cp*). These complexes were catalytically active in the cyclization of alkyne substrates with an intramolecular nucleophile (amine or alcohol) to produce 5- and 6-membered heterocycles. The effect of the 1° coordination sphere structure on catalyst performance was evaluated. Steric bulk around the metal centre was a key feature to achieve rapid catalysis at low temperatures. The catalyst [Ru(Cp)(PN)(MeCN)]PF gave a turnover number that was >1 order of magnitude more active than previous catalysts in the cyclization of the benchmark substrate 2-ethynylaniline. This catalyst is tolerant of a diversity of functional groups and is competent at the formation of various substituted indoles.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/c9dt01870k | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Bifunctional NiCo-CuO Nanostructures: A Promising Catalyst for Energy Conversion and Storage.
Small Methods
January 2025
Department of Physics, Tamkang University, Tamsui, 25137, Taiwan.
This investigation explores the potential of co-incorporating nickel (Ni) and cobalt (Co) into copper oxide (CuO) nanostructures for bifunctional electrochemical charge storage and oxygen evolution reactions (OER). A facile wet chemical synthesis method is employed to co-incorporate Ni and Co into CuO, yielding diverse nanostructured morphologies, including rods, spheres, and flake. The X-ray diffraction (XRD) and Raman analyses confirmed the formation of NiCo-CuO nanostructure, with minor phases of nickel oxide (NiO) and cobalt tetraoxide (CoO).
View Article and Find Full Text PDFGynura procumbensin vitro adventitious root nanohydrogel improves inflammation-proliferation transition in second-degree burn healing.
Braz J Biol
January 2025
Universitas Airlangga, Faculty of Science and Technology, Department of Biology, Mulyorejo, Surabaya, Indonesia.
Inflammation-proliferation transition plays a key role in the successful healing of a common burn type, second-degree burn. Gynura procumbens in vitro adventitious root nanohydrogel is currently being studied for its immunomodulatory to improve reparative environment. Root production and nanohydrogel preparation was done respectively by in vitro propagation and emulsion/ solvent diffusion with carbomer as a polymer.
View Article and Find Full Text PDFHow tailor-made copolymers can control the structure and properties of hybrid nanomaterials: the case of polyionic complexes.
Nanoscale
January 2025
Laboratoire Softmat, Université de Toulouse, CNRS UMR 5623, 118 route de Narbonne, 31062 Toulouse Cedex 9, France.
Hybrid polyionic complexes (HPICs) are colloidal structures with a charged core rich in metal ions and a neutral hydrophilic corona. Their properties, whether as reservoirs or catalysts, depend on the accessibility and environment of the metal ions. This study demonstrates that modifying the coordination sphere of these ions can tune the properties of HPICs by altering the composition of the complexing block or varying formulation conditions.
View Article and Find Full Text PDFChemoselectivity in Pd-Based Dyotropic Rearrangement: Development and Application in Total Synthesis of Pheromones.
J Am Chem Soc
January 2025
Laboratory of Synthesis and Natural Products (LSPN), Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, CH-1015 Lausanne, Switzerland.
In the dyotropic rearrangement of molecules with semiflexible structures, characterized by a freely rotating static C-C bond, the formation of a mixture of products is common due to the coexistence of several energetically comparable conformers. Herein, we report that it is possible to modulate the shifting groups by adjusting the metal's coordination sphere in Pd-based dyotropic rearrangement. In the presence of a catalytic amount of Pd(II) salt, the reaction of γ-hydroxyalkenes or γ,δ-dihydroxyalkenes with Selectfluor affords fluorinated tetrahydropyranols or 6,8-dioxabicyclo[3.
View Article and Find Full Text PDFModulation of the Second-Beyond Coordination Structure in Single-Atom Electrocatalysts for Confirmed Promotion of Ammonia Synthesis.
J Am Chem Soc
January 2025
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Although microenvironments surrounding single-atom catalysts (SACs) have been widely demonstrated to have a remarkable effect on their catalytic performances, it remains unclear whether the local structure beyond the secondary coordination shells works as well or not. Herein, we employed a series of metal-organic frameworks (MOFs) with well-defined and tunable second-beyond coordination spheres as model SAC electrocatalysts to discuss the influence of long-distance structure on the ammonia synthesis from nitrate, which were synthesized and denoted as Cu-NDI-X (X = NMe, H, F). It is first experimentally confirmed that the remote substitution of function groups beyond the secondary coordination sphere can remarkably affect the activity of ammonia synthesis.
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!