Exploring the Self-Assembled Tacticity in Aurophilic Polymeric Arrangements of Diphosphanegold(I) Fluorothiolates

Moreno‐Alcántar, Guillermo; Salazar, Laura Ann; Romo-Islas, Guillermo; Flores‐Álamo, Marcos; Torrens, Hugo

doi:10.3390/molecules24234422

Cited by 5 publications

(2 citation statements)

References 40 publications

(40 reference statements)

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“…Solvents were obtained from JT Baker (Thermo Fisher Scientific, Waltham, MA, USA) and used without previous treatment. Pb(SRF) 2 and AgSCF 3 were prepared as previously reported [46,47].…”

Section: Methodsmentioning

confidence: 99%

Fluorination Effects in XPhos Gold(I) Fluorothiolates

et al. 2021

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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.

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“…Solvents were obtained from JT Baker (Thermo Fisher Scientific, Waltham, MA, USA) and used without previous treatment. Pb(SRF) 2 and AgSCF 3 were prepared as previously reported [46,47].…”

Section: Methodsmentioning

confidence: 99%

Fluorination Effects in XPhos Gold(I) Fluorothiolates

et al. 2021

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“…Lead thiolates Pb(SR F ) 2 used in the synthesis of the compounds examined herein were obtained by the reaction of stoichiometrical amounts of aqueous lead acetate (Pb(CH 3 COO) 2 ) with a concentrated solution of the corresponding thiol in methanol, yielding a yellow or white (SR F = SC 6 HF 4 , SCH 2 CF 3 ) solid that was thoroughly washed with water and hexane. 61 Silver(I) trifluoromethylthiolate, obtained as described in ref 62, was used in the synthesis of 12 because of the instability of the lead analogue. The compound [AuCl(PPh 3 )] was obtained by the direct reaction of K[AuCl 4 ] with PPh 3 as reported by Fackler et al 63 The synthesis and characterization of compounds 1, 3, 11, and 12 were previously reported.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Directing the Crystal Packing in Triphenylphosphine Gold(I) Thiolates by Ligand Fluorination

et al. 2020

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3 . We use for this purpose (i) DFT electronic structure calculations and (ii) the quantum theory of atoms in molecules and the noncovalent interactions index methods of wave function analyses. Our combined experimental and computational approach yields a general understanding of the effects of ligand fluorination in the crystalline self-assembly of the examined systems, in particular, about the relative force of aurophilic contacts compared with other supramolecular interactions. We expect this information to be useful in the design of materials based on gold coordination compounds.

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