Category Ranking
98%
Total Visits
921
Avg Visit Duration
2 minutes
Citations
20
Article Abstract
Metal complexes with tunable ligands play a crucial role in olefin polymerization and impart control over molecular weight, crystallinity, and stereoregularity. We report the single-step synthesis of imine-phenoxy ligands in excellent yields (81-93%). The identity of electronically tuned imine-phenoxy ligands was unambiguously ascertained by using a combination of spectroscopic and analytical methods. These ligands were treated with [Pd(COD)MeCl] in the presence of 2,6-lutidine, resulting in the formation of discrete mononuclear palladium complexes Pd1-Pd4 in excellent yields. 1-2D NMR spectroscopy, mass spectrometry analysis, and single-crystal X-ray diffraction confirmed the identity of the palladium complexes. X-ray analysis revealed a distorted square planar geometry around the palladium center. Proton NMR analysis suggested that the Pd1 catalyst was deshielded, indicating electronically deficient palladium metal compared to the other complexes. Moreover, the Pd1 catalyst showed the highest buried volume percentage (%V = 44.9). When exposed to norbornene, Pd1-Pd4 were found to be active and produced poly(norbornene) (PNB). High-temperature SEC analysis revealed that the electronically deficient and sterically hindered Pd1 catalyst produced the highest molecular weight polymer (PNB 37.4 kDa). Boron and aluminum-based cocatalysts were screened, and MMAO was found to outperform others with high catalytic activity (up to 63.2 × 10 g of PNB (mol Pd) h).
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.inorgchem.4c04117 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Palladium-Catalyzed Coupling of Aryl Iodides with Sulfinamide Reagents for the Construction of Sulfinamides.
Chemistry
September 2025
Hainan Institute of East China Normal University, State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Process, School of Chemistry and Molecular Engineering, East China Normal University, 3663 North Zhongshan Rd., Shanghai, 20006
A novel sulfinamide reagent was developed that enables the one-step installation of sulfinamides through palladium-catalyzed coupling with aryl iodides. This method offers distinct advantages, including the use of readily available starting materials and broad substrate compatibility. Moreover, the strategy was successfully extended to the synthesis of complex functional molecules.
View Article and Find Full Text PDFCoordination-Driven Orthogonal Ligand Pairings through Dual Hydrogen-Bonding/π-π Interaction Complementarity.
Chemistry
September 2025
Research School of Chemistry, Australian National University, Canberra, ACT, 2610, Australia.
Multi-layered and orthogonal recognition is an excellent route to controlled molecular complexity. Here we report a series of heteroleptic complexes where two ligands pair together at a palladium(II) metal centre in complementary fashion and with orthogonality to others pairs. This complementarity is driven in part through hydrogen-bonding acceptor or donor sites proximal to the coordination domain (either DD:AA or AD:DA).
View Article and Find Full Text PDFSynthesis of Allylic Sulfones via Generation of Metal Π-Allyl Complexes in Metal-Catalyzed Sulfonylation.
Chem Rec
September 2025
College of Emergency Management, Chongqing Vocational Institute of Safety Technology, Wanzhou, Chongqing, 404020, P. R. China.
Allyl sulfones are common motifs in many drugs and natural products, exhibiting a wide range of biological activities such as anticancer and antibacterial properties, etc. An overview is provided on the synthesis of allylic sulfones via generation of metal π-allyl complexes in metal-catalyzed sulfonylation over the period from 2020 to the present. The generation process of metal π-allyl complexes is introduced from the perspective of reaction mechanism and the reaction processes such as nucleophilic substitution, insertion of SO, and reductive elimination involving metal π-allyl complexes is discussed.
View Article and Find Full Text PDFMixed-Length Multivariate Covalent Organic Framework for Combined Near-Infrared Photodynamic Therapy and Drug Delivery.
J Am Chem Soc
September 2025
Nanochemistry Department, Max Planck Institute for Solid State Research, Heisenbergstraße 1, 70569 Stuttgart, Germany.
Covalent organic frameworks (COFs) have been emerging as versatile reticular materials due to their tunable structures and functionalities, enabled by precise molecular engineering at the atomic level. While the integration of multiple components into COFs has substantially expanded their structural complexity, the strategic engineering of diverse functionalities within a single framework the random distribution of linkers with varying lengths remains largely unexplored. Here, we report a series of highly crystalline mixed-length multivariate COFs synthesized using azobenzene and bipyridine as linkers, where tuning the ratio of linkers and incorporating palladium effectively modulates the balance between near-infrared (NIR) light absorption and catalytic sites for NIR-generation of hydrogen peroxide (HO).
View Article and Find Full Text PDF-Bis[2-(pyrimidin-2-yl)ethyn-yl]bis-(tri-phenylphosphine)palladium.
IUCrdata
August 2025
Chemistry and Biochemistry Department, Missouri State University, 901 South National Avenue, Springfield MO 65897, USA.
The title palladium complex, [Pd(CHN)(CHP)], was isolated as an impurity that co-eluted with the organic product of a palladium-catalyzed Sonogashira coupling. It crystallizes in the monoclinic space group 2/ with one half of the complex in the asymmetric unit. The palladium atom (site symmetry ) has a square-planar geometry with phosphine ligands.
View Article and Find Full Text PDF