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Palladium-catalyzed fluoroalkylations of aryl halides are valuable reactions for the synthesis of fluorinated, biologically active molecules. Reductive elimination from an intermediate Pd(aryl)(fluoroalkyl) complex is the step that forms the C(aryl)–C(fluoroalkyl) bond, and this step typically requires higher temperatures and proceeds with slower rates than the reductive elimination of nonfluorinated alkylarenes from the analogous Pd(aryl)(alkyl) complexes. The experimental rates of this step correlate poorly with common parameters, such as the steric property or the electron-withdrawing ability of the fluoroalkyl ligand, making the prediction of rates and the rational design of Pd-catalyzed fluoroalkylations difficult. Therefore, a systematic study of the features of fluoroalkyl ligands that affect the barrier to this key step, including steric properties, electron-withdrawing properties, and secondary interactions, is necessary for the future development of fluoroalkylation reactions that occur under milder conditions and that tolerate additional types of fluoroalkyl reagents. We report computational studies of the effect of the fluoroalkyl (RF) ligand on the barriers to reductive elimination from Pd(aryl)(RF) complexes (RF = CF2CN, CF2C(O)Me, etc.) containing the bidentate ligand di-tert-butyl(2-methoxyphenyl)phosphine (L). The computed Gibbs free-energy barriers to reductive elimination from these complexes suggest that fluoroalkylarenes should form quickly at room temperature for the fluoroalkyl ligands we studied, excluding RF = CF3, CF2Me, C2F5, CF2CFMe2, CF2Et, CF2iPr, or CF2tBu. Analyses of the transition-state structures by natural bond orbital (NBO) and independent gradient model (IGMH) approaches reveal that orbital interactions between the Pd center and a hydrogen atom or π-acid bonded to the α-carbon atom of the RF ligand stabilize the lowest-energy transition states of Pd(aryl)(RF) complexes. Comparisons between conformers of transition-state structures suggest that the magnitude of such stabilizations is 4.7–9.9 kcal/mol. In the absence of these secondary orbital interactions, a more electron-withdrawing fluoroalkyl ligand leads to a higher barrier to reductive elimination than a less electron-withdrawing fluoroalkyl ligand. Computations on the reductive elimination from complexes containing para-substituted aryl groups on palladium reveal that the barriers to reductive elimination from complexes containing more electron-rich aryl ligands tend to be lower than those to reductive elimination from complexes containing less electron-rich aryl ligands when the fluoroalkyl ligands of these complexes can engage in secondary orbital interactions with the metal center. However, the computed barriers to reductive elimination do not depend on the electronic properties of the aryl ligand when the fluoroalkyl ligands do not engage in secondary orbital interactions with the metal center.
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Bimetallic copper palladium nanorods: plasmonic properties and palladium content effects
Cu is an inexpensive alternative plasmonic metal with optical behaviour comparable to Au but with much poorer environmental stability. Alloying with a more stable metal can improve stability and add functionality, with potential effects on the plasmonic properties. Here we investigate the plasmonic behaviour of Cu nanorods and Cu–CuPd nanorods containing up to 46 mass percent Pd. Monochromated scanning transmission electron microscopy electron energy-loss spectroscopy first reveals the strong length dependence of multiple plasmonic modes in Cu nanorods, where the plasmon peaks redshift and narrow with increasing length. Next, we observe an increased damping (and increased linewidth) with increasing Pd content, accompanied by minimal frequency shift. These results are corroborated by and expanded upon with numerical simulations using the electron-driven discrete dipole approximation. This study indicates that adding Pd to nanostructures of Cu is a promising method to expand the scope of their plasmonic applications.
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- Award ID(s):
- 2239441
- PAR ID:
- 10473159
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Nanoscale Advances
- ISSN:
- 2516-0230
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D3NA00523B
