Abstract
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.
Highlights
Gold chemistry has emerged as one of the most interesting, fruitful, and promising trends in coordination and organometallic chemistry [1,2,3]
The modification of the fluorination pattern into this series of thiolate gold(I) derivatives including the Buchwald phosphine XPhos has shown to exert a substantial modulation over the type and intensity of the intra- and inter-molecular non-covalent interactions formed by these compounds
The theoretical and topological study of the crystallographic structures, via the quantum theory of atoms in molecules (QTAIM) and the NCI-index, allowed us to characterize the properties of the studied systems in a more comprehensive way than that based on a sole geometrical analysis
Summary
Gold chemistry has emerged as one of the most interesting, fruitful, and promising trends in coordination and organometallic chemistry [1,2,3]. The catalytical activity of gold compounds has open new routes to fine chemicals of commercial relevance [20,21]. Gold(I) compounds of Buchwald phosphane ligands [22] have been lately used in catalytic transformations [20,23,24]. SSyynntthheettiicc sscchheemmee aanndd ssttrruuccttuurreess ooff tthhee 1122 [[AAuuSSRRFF((XXPPhhooss))]]ccoommppoouunnddss pprreesseenntteedd iinn tthhiiss wwoorrkk. Compounds 7 and 12 display two independent molecular structures in the asymmetric unit; two sets of data are displayed. In these cases, the differences between the two conformers in the crystal are small in compound 7 and more noticeable in compound 12.
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