π-Backbonding and non-covalent interactions in the JohnPhos and polyfluorothiolate complexes of gold(<scp>i</scp>)

Moreno‐Alcántar, Guillermo; Hess, Kristopher M.; Guevara‐Vela, José Manuel; Rocha‐Rinza, Tomás; Pendás, Ángel Martín; Flores‐Álamo, Marcos; Torrens, Hugo

doi:10.1039/c7dt00961e

Cited by 9 publications

(18 citation statements)

References 51 publications

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“…We performed all the electronic structure calculations in the ORCA program . This methodology has been successfully employed in the description of metal‐metal as well as metal‐ligand bonding by others and in our own research , . The Quantum Theory of Atoms in Molecules (QTAIM) methodology was used to investigate the chemical bonding scenario in the examined systems.…”

Section: Methodsmentioning

confidence: 99%

“…[54] This methodology has been successfully employed in the description of metal-metal as well as metal-ligand bonding by others [55][56][57] and in our own research. [58,59] The Quantum Theory of Atoms in Molecules (QTAIM) methodology was used to investigate the chemical bonding scenario in the examined systems. QTAIM is a wave function analysis approach based on the topology of the charge distribution ρ(r) and results in an exhaustive partition of space into disjoint regions that can be identified with the atoms of chemistry.…”

Section: Synthesismentioning

confidence: 99%

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Stability andtransInfluence in Fluorinated Gold(I) Coordination Compounds

et al. 2018

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We examined the Au–P and Au–X chemical bonding scenario throughout the series of compounds of the general formula [AuX(LP)] wherein LP is triphenylphosphine or a fluorinated phosphine [PPhF = P(C6H5)2(C6F5) 1, P(C6H5)(C6F5)2 2 and P(C6F5)3 3] and X is chloride or a fluorinated thiolate [SRF = SCF3 a, SCH2CF3 b, SC6F5 c, SC6F4(CF3)‐4 d]. We found that the increase of the fluorination degree or the replacement of Cl– by a –SRF ligand decreases the stability of the compound. Furthermore, this substitution shifts the 31P‐NMR signals to low field, which indicates differences in the electronegativity of the phosphorus due to the distinct trans influences of the Cl– and –SRF species. These effects correlate with the charge of the gold atom coordinated to phosphorus. Our investigation shows the high potential of fluorination as a strategy for the modulation of the properties of gold compounds, for example in catalysis, and the applicability of quantum chemical topology studies in the explanation of these features.

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Section: Methodsmentioning

confidence: 99%

Section: Synthesismentioning

confidence: 99%

Stability andtransInfluence in Fluorinated Gold(I) Coordination Compounds

et al. 2018

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“…The incidence of intramolecular Au-arene contacts in Buchwald-type gold complexes has attracted considerable attention [32,[34][35][36]. To characterize these interactions within this family of compounds, we have used the Au-π distance (i.e., the distance between the gold center and the plane generated by the capping phenyl ring).…”

Section: Au-arene Contactsmentioning

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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“…The topological analyses of the electron density within the formalism of Quantum Chemical Topology (QCT) have offered valuable insights about many processes in chemistry [41–44] . More specifically, wave function analyses as defined by the Quantum Theory of Atoms in Molecules (QTAIM) [45] have been extensively exploited to examine the basic features of the interactions within clusters of different composition.…”

Section: Introductionmentioning

confidence: 99%

“…[24,[38][39][40] The topological analyses of the electron density within the formalism of Quantum Chemical Topology (QCT) have offered valuable insights about many processes in chemistry. [41][42][43][44] More specifically, wave function analyses as defined by the Quantum Theory of Atoms in Molecules (QTAIM) [45] have been extensively exploited to examine the basic features of the interactions within clusters of different composition. Among different options in the QCT partitioning of the electronic energy in the context of Kohn-Sham theory, the Interacting Quantum Atoms (IQA) method [46,47] yields the best results regarding the nature of distinct chemical bonds, e. g., intermolecular interactions which is the main topic of this paper.…”

Section: Introductionmentioning

confidence: 99%

Cooperativity and Anticooperativity in Ion‐Water Interactions: Implications for the Aqueous Solvation of Ions

2021

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Non‐additive effects in hydrogen bonds (HB) take place as a consequence of electronic charge transfers. Therefore, it is natural to expect cooperativity and anticooperativity in ion‐water interactions. Nevertheless, investigations on this matter are scarce. This paper addresses the interactions of (i) the cations Li+, Na+, K+, Be2+, Mg2+, and Ca2+ together with (ii) the anions F−, Cl−, Br−, NO3− and SO42− with water clusters (H2O)n, n=1–8, and the effects of these ions on the HBs within the complete molecular adducts. We used quantum chemical topology tools, specifically the quantum theory of atoms in molecules and the interacting quantum atoms energy partition to investigate non‐additive effects among the interactions studied herein. Our results show a decrease on the interaction energy between ions and the first neighbouring water molecules with an increment of the coordination number. We also found strong cooperative effects in the interplay between HBs and ion‐dipole interactions within the studied systems. Such cooperativity affects considerably the interactions among ions with their first and second solvation shells in aqueous environments. Overall, we believe this article provides valuable information about how ion‐dipole contacts interact with each other and how they relate to other interactions, such as HBs, in the framework of non‐additive effects in aqueous media.

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π-Backbonding and non-covalent interactions in the JohnPhos and polyfluorothiolate complexes of gold(i)

Cited by 9 publications

References 51 publications

Stability andtransInfluence in Fluorinated Gold(I) Coordination Compounds

Stability andtransInfluence in Fluorinated Gold(I) Coordination Compounds

Fluorination Effects in XPhos Gold(I) Fluorothiolates

Cooperativity and Anticooperativity in Ion‐Water Interactions: Implications for the Aqueous Solvation of Ions

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