Bond Analysis in Dihalogen–Halide and Dihalogen–Dimethylchalcogenide Systems

Schneider, Felipe S. S.; Caramori, Giovanni F.; Parreira, Renato L. T.; Lippolis, Vito; Arca, Massimiliano; Ciancaleoni, Gianluca

doi:10.1002/ejic.201701337

Cited by 8 publications

(7 citation statements)

References 75 publications

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“…Not only that but all the heterotrihalides behave similarly, with a small systematic difference depending on the different polarizability of the systems. For neutral systems involving chalcogen atoms, the CT function has again the same general shape but the extent of the polarization is much lower (0.261 instead of 0.400 e) [62]. Also in this case, the nature of E or X has a little influence on the value of CT, which depends only on the normalized distances.…”

Section: Condensed Phasementioning

confidence: 74%

“…Therefore, the two topics have been unified in a recent contribution [37]. As a case study, [(NAC)Au(SeU)]BF 4 (NAC = nitrogen acyclic carbene, SeU = selenourea) has been chosen-the selenium can establish XB with polarized halogen atoms [58,62,67], the NAC is an experimental probe for Au → C back-donation, due to the inverse proportionality between the latter and the C-N rotational barrier [27].…”

Section: Condensed Phasementioning

confidence: 99%

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Charge Displacement Analysis—A Tool to Theoretically Characterize the Charge Transfer Contribution of Halogen Bonds

Ciancaleoni

Nunzi

Belpassi³

2020

Molecules

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Theoretical bonding analysis is of prime importance for the deep understanding of the various chemical interactions, covalent or not. Among the various methods that have been developed in the last decades, the analysis of the Charge Displacement function (CD) demonstrated to be useful to reveal the charge transfer effects in many contexts, from weak hydrogen bonds, to the characterization of σ hole interactions, as halogen, chalcogen and pnictogen bonding or even in the decomposition of the metal-ligand bond. Quite often, the CD analysis has also been coupled with experimental techniques, in order to give a complete description of the system under study. In this review, we focus on the use of CD analysis on halogen bonded systems, describing the most relevant literature examples about gas phase and condensed phase systems. Chemical insights will be drawn about the nature of halogen bond, its cooperativity and its influence on metal-ligand bond components.

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Section: Condensed Phasementioning

confidence: 74%

Section: Condensed Phasementioning

confidence: 99%

Charge Displacement Analysis—A Tool to Theoretically Characterize the Charge Transfer Contribution of Halogen Bonds

Ciancaleoni

Nunzi

Belpassi³

2020

Molecules

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“…Binding energy (ΔE bind ) between α-CD and guest in the implicit SMD water was obtained with the supermolecule approach by subtracting the energy of isolated host and guest molecules from that of bound complexes. Based on the so-called chemist's grouping, ΔE bind by SAPT0 calculations is decomposed into electrostatics (ΔE elst ), exchange (ΔE exch ), induction (ΔE ind ), and dispersion (ΔE disp ) terms, 54,55,68 and an empirical scaled SAPT0 (sSAPT0) interaction energy was used for improved performance, as shown by Parker et al 58 The charge-transfer energy (ΔE CT ) is a part of the induction term and was computed using the method by Stone and Misquitta. 57 From PMF profiles of ΔG(ξ), standard binding free energy (ΔG calc 0 ) can be computed with a cylinder approximation (eq 1) 62,69−71…”

Section: Methodsmentioning

confidence: 99%

Role of Host–Guest Charge Transfer in Cyclodextrin Complexation: A Computational Study

et al. 2019

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Charge transfer (CT) was proposed to play a role in the cyclodextrin (CD) complexation with guest molecules. To elucidate the importance of CT interactions, here we used computational methods of quantum mechanics, docking, and molecular dynamics (MD) to investigate α-CD complexes with aromatic guest molecules of nitrobenzene, carboxybenzene, benzoate, 4-nitrophenol, and 4-nitrophenolate. Considering host−guest CT in the docking has more of a chance to search reasonable guest orientations relative to α-CD matching the experiment, compared to that without CT. The CT interaction enlarges the difference in binding affinities of varied guests, as evidenced from potential of mean force (PMF) MD calculations. Energy decomposition of the total enthalpy and entropy shows the CT influence on the binding reactions in detail and indicates that there are considerable compensating effects of individual contributions from the binding partners and surrounding water. Charge transfer reduces the total dipole of α-CD by 9% on average and alters its dipole direction thereby affecting guest association. Gas-phase zeroth-order symmetry-adapted perturbation theory calculations show host−guest CT amounts to approximately 6% of the total binding energy. The continuum solvation model based on the quantum mechanical charge density predicts binding energies comparable with the well depth of PMF profiles in explicit water. The abnormal binding strength of α-CD with the similar guests can be rationalized in terms of hydrogen bonding, extent of host−guest CT, and dipole arrangement of guest relative to host.

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“…More specifically, the presence of a noncovalent interaction can influence the covalency of a chemical bond. For example, when I 2 establishes a halogen bond, the I–I bond lengthens until, in the extreme cases, it breaks and becomes a halogen bond itself. , In a similar way, the C–Se bond order in selenourea is influenced by the presence of the hydrogen bond (HB) acceptors …”

Section: Introductionmentioning

confidence: 99%

Interplay between Gold(I)-Ligand Bond Components and Hydrogen Bonding: A Combined Experimental/Computational Study

2019

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The influence of weak interactions on the donation/back-donation bond components in the complex [(NHC)Au( SeU )] + (NHC = N-heterocyclic carbene; SeU = selenourea) has been studied by coupling experimental and theoretical techniques. In particular, NMR 1 H and pulsed-field gradient spin-echo titrations allowed us to characterize the hydrogen bond (HB) between the −NH 2 moieties of SeU and the anions PF 6 – and ClO 4 – , whereas 77 Se NMR spectroscopy allowed us to characterize the Au–Se bond. Theoretically, the Au–Se and Au–C orbital interactions have been decomposed using the natural orbital for the chemical valence framework and the bond components quantified through the charge displacement analysis. This methodology provides the quantification of the Dewar–Chatt–Duncanson (DCD) components for the Au–C and Au–Se bonds in the absence and presence of the second-sphere HB. The results presented here show that the anion has a dual mode action: it modifies the conformation of the cation by ion pairing (and this already influences the DCD components) and it induces new polarization effects that depend on the relative anion/cation relative orientation. The perchlorate polarizes SeU , enhancing the Se → Au σ donation and the Au → C back-donation and depressing the C → Au σ donation. On the contrary, the hexafluorophosphate depresses both the Se → Au and C → Au σ donations.

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Bond Analysis in Dihalogen–Halide and Dihalogen–Dimethylchalcogenide Systems

Cited by 8 publications

References 75 publications

Charge Displacement Analysis—A Tool to Theoretically Characterize the Charge Transfer Contribution of Halogen Bonds

Charge Displacement Analysis—A Tool to Theoretically Characterize the Charge Transfer Contribution of Halogen Bonds

Role of Host–Guest Charge Transfer in Cyclodextrin Complexation: A Computational Study

Interplay between Gold(I)-Ligand Bond Components and Hydrogen Bonding: A Combined Experimental/Computational Study

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