We report that surrounding coordination of neutral six-membered arene rings affords molecularly well-defined organotransition metal nanoclusters. With the use of [2.2]paracyclophane as the face-capping arene ligand, we have isolated two polyarene palladium nanoclusters, one consisting of a hexakis-arene ligand shell and a hexagonal close-packed Pd anticuboctahedron trichloride core, and the other consisting of an octakis-arene ligand shell and a non-close-packed Pd square gyrobicupola dichloride core, both with Pd-Pd direct bonding. The μ-facial coordination mode of arene was discovered through the structural characterization of the Pd cluster. Their Pd and Pd cores, which are distinct from the previously identified face-centered-cubic Pd core surrounded by seven-membered cycloheptatrienyl, are explained by stereochemical and theoretical analyses.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10360153 | PMC |
| http://dx.doi.org/10.1021/jacs.3c02849 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Palladium-catalyzed asymmetric carbene coupling en route to inherently chiral heptagon-containing polyarenes.
Nat Commun
April 2024
College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, 266071, China.
Developing facile and direct synthesis routes for enantioselective construction of cyclic π-conjugated molecules is crucial. However, originate chirality from the distorted structure around heptagon-containing polyarenes is largely overlooked, the enantioselective construction of all-carbon heptagon-containing polyarenes remains a challenge. Herein, we present a highly enantioselective synthesis route for fabricating all carbon heptagon-containing polyarenes via palladium-catalyzed carbene-based cross-coupling of benzyl bromides and N-arylsulfonylhydrazones.
View Article and Find Full Text PDFDeveloping Biarylhemiboronic Esters for Biaryl Atropisomer Synthesis via Dynamic Kinetic Atroposelective Suzuki-Miyaura Cross-Coupling.
J Am Chem Soc
March 2024
Department of Chemistry, School of Science, China Pharmaceutical University, Nanjing 211198, P. R. China.
Article Synopsis
- Biarylhemiboronic esters are introduced as a new reagent for creating axially chiral biaryl structures through palladium-catalyzed asymmetric Suzuki-Miyaura cross-coupling.
- This method shows high enantioselectivity, can tolerate a variety of functional groups, and works well with a wide range of substrates.
- Initial mechanistic studies indicate that the reaction involves an enantio-determining dynamic kinetic step during the transmetalation process.
Synthesis of Heptagon-Containing Polyarenes by Catalytic C-H Activation.
Angew Chem Int Ed Engl
December 2023
Department of Chemistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan.
Nanocarbons incorporating non-hexagonal aromatic rings - such as five-, seven-, and eight-membered rings - have various intriguing physical properties such as curved structures, unique one-dimensional packing, and promising magnetic, optical, and conductivity properties. Herein, we report an efficient synthetic approach to polycyclic aromatics containing seven-membered rings via a palladium-catalyzed intramolecular Ar-H/Ar-Br coupling. In addition to all-hydrocarbon scaffolds, heteroatom-embedded heptagon-containing polyarenes can be efficiently constructed with this method.
View Article and Find Full Text PDFIsolation and Structures of Polyarene Palladium Nanoclusters.
J Am Chem Soc
July 2023
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8552, Japan.
We report that surrounding coordination of neutral six-membered arene rings affords molecularly well-defined organotransition metal nanoclusters. With the use of [2.2]paracyclophane as the face-capping arene ligand, we have isolated two polyarene palladium nanoclusters, one consisting of a hexakis-arene ligand shell and a hexagonal close-packed Pd anticuboctahedron trichloride core, and the other consisting of an octakis-arene ligand shell and a non-close-packed Pd square gyrobicupola dichloride core, both with Pd-Pd direct bonding.
View Article and Find Full Text PDFPalladium Mediated Synthesis of Protein-Polyarene Conjugates.
J Am Chem Soc
July 2022
Massachusetts Institute of Technology, Department of Chemistry, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
Catalyst transfer polymerization (CTP) is widely applied to the synthesis of well-defined π-conjugated polymers. Unlike other polymerization reactions that can be performed in water (e.g.
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!