Fluorination Effects in XPhos Gold(I) Fluorothiolates

• Published in: Inorganics Vol. 9; no. 2; p. 14
• Main Authors: Moreno-Alcántar, Guillermo, Díaz-Rosas, Cristian, Fernández-Alarcón, Alberto, Turcio-García, Luis, Flores-Álamo, Marcos, Rocha-Rinza, Tomás, Torrens, Hugo
• Format: Journal Article
• Language: English
• Published: Basel MDPI AG 01.02.2021
• Subjects: Buchwald ligands; Carbon; Catalysts; Catalytic activity; Chemistry; Derivatives; fluorinated thiolates; Fluorination; Gold; gold complexes; Ligands; NMR; non-covalent interactions; Nuclear magnetic resonance; Packaging; Phosphine; Phosphines; QTAIM; Quantum chemistry; Quantum theory; Topology
• ISSN: 2304-6740; 2304-6740
• DOI: 10.3390/inorganics9020014

Gold phosphine derivatives such as thiolates have been recently proposed as catalysts or catalyst precursors. The relevance of the supramolecular environment on the fine-tuning of the catalytical activity on these compounds incentivizes the use of tools that are convenient to characterize in detail the non-covalent landscape of the systems. Herein, we show the molecular and supramolecular diversity caused by the changes in the fluorination pattern in a family of new XPhos goldfluorothiolate derivatives. Furthermore, we studied the supramolecular interactions around the Au centers using quantum chemical topology tools, in particular the quantum theory of atoms in molecules (QTAIM) and the non-covalent interaction index. Our results give detailed insights into the fluorination effects on the strength of intramolecular and intermolecular interactions in these systems. We have also used QTAIM delocalization indexes to define a novel hapticity indicator. Finally, we assessed the trans influence of the fluorothiolates on the phosphine in terms of the change in the δ 31P-NMR. These results show the feasibility of the use of fluorination in the modulation of the electronic properties of Buchwald phosphine gold(I) compounds, and thereby its potential catalytic activity.