Spectroscopy of Halogen Bonding in Solution

Wilcox, Scott; Herrebout, Wouter A.; Erdélyi, Máté

doi:10.1002/9783527825738.ch5

Cited by 8 publications

(11 citation statements)

References 138 publications

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“…Unfortunately, because solid matrices are not in thermodynamic equilibrium, no direct information about the relative stability of the species can be deduced. This shortcoming can be avoided by studying the complexes in cryogenic solutions [64][65][66]. Apart from the relatively low temperatures used during these experiments and the weak solutesolvent interactions present, a major advantage of these cryosolutions is their transparency in a broad spectral interval, ranging from the far-IR to the ultraviolet.…”

Section: Methodology and Experimental And Computational Detailsmentioning

confidence: 99%

“…Solutions in liquefied inert gases have also proven to be an ideal medium to study the spectroscopic and thermodynamic properties of molecular complexes held together by weak red-or blue-shifting C-H•••X hydrogen bonds or weak and medium-strong C−X•••Y (with X = I, Br, Cl and Y = O, N, S, F, Cl, π, and so on) halogen bonds. The experimental setups for the infrared and Raman studies of cryosolutions and general methodologies used to characterize these molecular complexes observed have been reviewed in depth [64][65][66][67], and will thus not be discussed in detail here.…”

Section: Methodology and Experimental And Computational Detailsmentioning

confidence: 99%

“…The experimental values derived from cryo-solutions should thus not be directly compared with ab initio complexation energies or vapor phase complexation enthalpies. To correct for solvent effects, and to obtain a vapor phase complexation enthalpy, for all species involved, the solvation processes in liquid rare gases were simulated using Monte Carlobased free energy perturbation calculations using the same procedures as those described before [64][65][66].…”

Section: Methodology and Experimental And Computational Detailsmentioning

confidence: 99%

“…Estimated mole fractions of the solutions varied between 1 × 10 −5 and 1 × 10 −3 for the Lewis bases DME and TMA and between 1 × 10 −6 and 8 × 10 −4 for the Lewis acids 12 CO 2 , 13 CO 2 , N 2 O, and OCS. As the experimental setups do not allow for verification of full solubility of the compounds, or verification of the fluid level in the filling tube [64][65][66], exact concentrations are not known.…”

Section: Methodsmentioning

confidence: 99%

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A Combined Experimental/Quantum-Chemical Study of Tetrel, Pnictogen, and Chalcogen Bonds of Linear Triatomic Molecules

et al. 2021

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Linear triatomic molecules (CO2, N2O, and OCS) are scrutinized for their propensity to form perpendicular tetrel (CO2 and OCS) or pnictogen (N2O) bonds with Lewis bases (dimethyl ether and trimethyl amine) as compared with their tendency to form end-on chalcogen bonds. Comparison of the IR spectra of the complexes with the corresponding monomers in cryogenic solutions in liquid argon enables to determine the stoichiometry and the nature of the complexes. In the present cases, perpendicular tetrel and pnictogen 1:1 complexes are identified mainly on the basis of the lifting of the degenerate ν 2 bending mode with the appearance of both a blue and a red shift. Van ′t Hoff plots of equilibrium constants as a function of temperature lead to complexation enthalpies that, when converted to complexation energies, form the first series of experimental complexation energies on sp1 tetrel bonds in the literature, directly comparable to quantum-chemically obtained values. Their order of magnitude corresponds with what can be expected on the basis of experimental work on halogen and chalcogen bonds and previous computational work on tetrel bonds. Both the order of magnitude and sequence are in fair agreement with both CCSD(T) and DFA calculations, certainly when taking into account the small differences in complexation energies of the different complexes (often not more than a few kJ mol−1) and the experimental error. It should, however, be noted that the OCS chalcogen complexes are not identified experimentally, most probably owing to entropic effects. For a given Lewis base, the stability sequence of the complexes is first successfully interpreted via a classical electrostatic quadrupole–dipole moment model, highlighting the importance of the magnitude and sign of the quadrupole moment of the Lewis acid. This approach is validated by a subsequent analysis of the molecular electrostatic potential, scrutinizing the σ and π holes, as well as the evolution in preference for chalcogen versus tetrel bonds when passing to “higher” chalcogens in agreement with the evolution of the quadrupole moment. The energy decomposition analysis gives further support to the importance/dominance of electrostatic effects, as it turns out to be the largest attractive term in all cases considered, followed by the orbital interaction and the dispersion term. The natural orbitals for chemical valence highlight the sequence of charge transfer in the orbital interaction term, which is dominated by an electron-donating effect of the N or O lone-pair(s) of the base to the central atom of the triatomics, with its value being lower than in the case of comparable halogen bonding situations. The effect is appreciably larger for TMA, in line with its much higher basicity than DME, explaining the comparable complexation energies for DME and TMA despite the much larger dipole moment for DME.

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Section: Methodology and Experimental And Computational Detailsmentioning

confidence: 99%

Section: Methodology and Experimental And Computational Detailsmentioning

confidence: 99%

Section: Methodology and Experimental And Computational Detailsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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A Combined Experimental/Quantum-Chemical Study of Tetrel, Pnictogen, and Chalcogen Bonds of Linear Triatomic Molecules

et al. 2021

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“…The halogen bond (X-bond) in solution [16][17][18][19][20][21] has recently drawn considerable attention owing to the similarity of its electrostatic property to that of the H-bond in solution. The two-center-two-electron (2c2e) bond-based interactions are the most common features in both the H-and X-bonds: the positive charge of a hydrogen atom or a small region of positive charge on the terminus of a halogen atom can interact with the negative charge of an electron-rich species (Fig.…”

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confidence: 99%

Three-center-four-electron halogen bond enables sub-ppm-level non-metallic complex catalysis

Oishi

Fujinami

MASUI

et al. 2022

Preprint

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The three-center-four-electron halogen bond (3c4e X-bond) presents a new design concept for catalysis. By integrating halogen(I) (X+: I+ or Br+), bis-pyridyl ligand NN, and non-nucleophilic counter anion Y. [N···X···N]SbF6, we developed non-metallic complex catalysts, [N···X···N]Ys, which exhibited outstanding activity and facilitated the Mukaiyama–Mannich-type reaction of N-heteroaromatics with sub-ppm-level catalyst loading. The high activity of [N···X···N]SbF6 was clearly demonstrated. NMR titration experiments, CSI-MS, computations, and UV-vis spectroscopic studies attribute the robust catalytic activity of [N···X···N]Y to the unique feature of the 3c4e X-bond for binding chloride: i) the partial covalent nature transforms [N···X···N]+ complexation to sp2CH as a hydrogen bonding donor site, and ii) the noncovalent property allows for the dissociation of [N···X···N]+ for the formation of [Cl···X···Cl]–. This study introduces a new application of 3c4e X-bonds to catalysis via halogen(I) complexes.

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Pushing the Limits of Characterising a Weak Halogen Bond in Solution

Peintner

Erdélyi

2021

Chemistry A European J

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Detection and characterisation of very weak, noncovalent interactions in solution is inherently challenging. Low affinity, short complex lifetime and a constant battle against entropy brings even the most sensitive spectroscopic methods to their knees. Herein we introduce a strategy for the accurate experimental description of weak chemical forces in solution. Its scope is demonstrated by the detailed geometric and thermodynamic characterisation of the weak halogen bond of a non-fluorinated aryl iodide and an ether oxygen (0.6 kJ mol À 1 ). Our approach makes use of the entropic advantage of studying a weak force intramolecularly, em-bedded into a cooperatively folding system, and of the combined use of NOE-and RDC-based ensemble analyses to accurately describe the orientation of the donor and acceptor sites. Thermodynamic constants (ΔG, ΔH and ΔS), describing the specific interaction, were derived from variable temperature chemical shift analysis. We present a methodology for the experimental investigation of remarkably weak halogen bonds and other related weak forces in solution, paving the way for their improved understanding and strategic use in chemistry and biology.

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Spectroscopy of Halogen Bonding in Solution

Cited by 8 publications

References 138 publications

A Combined Experimental/Quantum-Chemical Study of Tetrel, Pnictogen, and Chalcogen Bonds of Linear Triatomic Molecules

A Combined Experimental/Quantum-Chemical Study of Tetrel, Pnictogen, and Chalcogen Bonds of Linear Triatomic Molecules

Three-center-four-electron halogen bond enables sub-ppm-level non-metallic complex catalysis

Pushing the Limits of Characterising a Weak Halogen Bond in Solution

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