2024-03-29T14:24:10Zhttps://uvadoc.uva.es/oai/requestoai:uvadoc.uva.es:10324/453282021-06-24T07:44:16Zcom_10324_28542com_10324_952com_10324_894col_10324_28543
UVaDOC
author
Ponce de León Pintado, Jaime
author
Infante Blanco, Rebeca
author
Pérez Iglesias, María
author
Espinet Rubio, Pablo
2021-02-22T12:32:28Z
2021-02-22T12:32:28Z
2020
Inorganic Chemistry, 2020, 59, 22, 16599–16610
0020-1669
http://uvadoc.uva.es/handle/10324/45328
10.1021/acs.inorgchem.0c02513
16599
22
16610
Inorganic Chemistry
59
1520-510X
Six fluorinated PR2(biaryl) phosphines, Ln, with R = Ph, Cy and biaryl = C6H4–C6F5, C6F4–C6H5, C6F4–C6F5, have been prepared. Their [AuCl(Ln)] complexes and H congeners with PhJohnPhos or CyJohnPhos have been studied in order to examine the interactions that bring the distal aryl close to the Au–Cl bond region. X-ray, DFT structure optimization, QTAIM, and NCI methods allow for some understanding of the forces involved. The “no bond” noncovalent distal-aryl/Au–Cl weak interactions are produced at forced short distances achieved under intramolecular structural ligand pressure. Enhanced vdW distal-aryl/Au interactions at “no bond” distances shorter than the sum of Au and C vdW radii and weaker distal-aryl/Cl interactions at “no bond” distances beyond the sum of Cl and C vdW radii counterbalance the unfavorable structural distortion of the free ligand, providing some extra stability of the molecule on the order of 2–10 kcal mol–1. The F substituents in the distal aryl induce shorter aryl distances to the Au–Cl zone, pointing overall to stronger π-aryl polarization as being mainly responsible for the NCIs with gold. The interactions in the C···Cl zone, where the distances are larger than the sum of vdW radii, contribute only about 5%, according to energy estimations using NBOs.
eng
Attribution-NonCommercial-NoDerivatives 4.0 Internacional
Fluorinated vs Nonfluorinated PR2(biaryl) Ligands and Their [AuCl(L)] Complexes: Synthesis, X-ray Structures, and Computational Study of Weak Interactions. Bond, No Bond, and Beyond
info:eu-repo/semantics/article
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URL
https://uvadoc.uva.es/bitstream/10324/45328/1/Fluorinated%20vs.%20Non-fluorinated.pdf
File
MD5
ef3f3cca77ceaa4e4117a449fcf84d36
7191021
application/pdf
Fluorinated vs. Non-fluorinated.pdf