Phosphine oxides as NMR and IR spectroscopic probes for the estimation of the geometry and energy of PO⋯H–A hydrogen bonds

Kostin, M.; Pylaeva, Svetlana; Tolstoy, Peter M.

doi:10.1039/d1cp05939d

Cited by 6 publications

(10 citation statements)

References 90 publications

(91 reference statements)

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“…Convincingly, recent studies have shown that the strength of hydrogen bonding of Et 3 P=O with Brønsted acids is correlated with the pKa value of the acid. [113][114][115][116] which underlines the significance of Figure 8 and Equation (36a). Consequently, the linear correlation of ν max (Fe) with AN observed in the order ethanol (pKa = 18), acetic acid (pKa = 4.7), formic acid (pKa = 3.75) and trifluoroacetic acid (pKa = 0.52), as shown in Ref.…”

Section: Chemphyschemsupporting

confidence: 57%

“…Various researches have been carried out in the literature on the construction of AN scales in relation to Gutmann‘s AN using using 31 P NMR sensitive probes different from Et3P=O [112–116] . However, these alternative AN ‐scales have not proved successful for organic solvents, see Equation (S25) in SI [112] .…”

Section: Final Discussion On Et(30)mentioning

confidence: 99%

“…[111] Various researches have been carried out in the literature on the construction of AN scales in relation to Gutmann's AN using using 31 P NMR sensitive probes different from Et3P = O. [112][113][114][115][116] However, these alternative AN-scales have not proved successful for organic solvents, see Equation (S25) in SI. [112] In accordance to the results of the other probes, the large AN value for water (AN = 54.8, pK a = 15.75 at T = 25 °C) is clearly attributed to the large molar concentration (55.45 mol/L) and not to hydrogen bond acidity, because water fits well in Equation (35) (see Figure 7 and Figure S23, SI).…”

Section: Chemphyschemmentioning

confidence: 99%

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Empirical Hydrogen Bonding Donor (HBD) Parameters of Organic Solvents Using Solvatochromic Probes – A Critical Evaluation

Spange

Weiß

2023

ChemPhysChem

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The solvatochromicity of established solvatochromic UV/Vis probes, which appear to be sensitive to the so-called hydrogen bond donor (HBD) property of the solvent, is analysed using the hydroxyl group density of alcoholic solvents D HBD as a physical parameter in comparison to the pKa, the chemical benchmark for acidity. Reichardt's dye B30, Kosowers Z-indicator 1-ethyl-4-(methoxycarbonyl) pyridinium iodide (K), Kamlet-Tafts α, Dragos S parameter, Catalans SA scale, the cis-dicyano-bis (1,10phenanthroline) iron II complex (Schilt's Ferrocyphen dye, Fe) and Gutmann's acceptor number (AN) have been investigated. The observed dependencies of the empirical polarity parameters as a function of D HBD for several alcoholic solvent families requires a ompletely new physicochemical understanding of these established HBD parameters. Only the AN scale (or Fe) is able to bridge the gap between global polarity and acidity, provided the values are interpreted correctly and applied accordingly.

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Section: Chemphyschemsupporting

confidence: 57%

Section: Final Discussion On Et(30)mentioning

confidence: 99%

Section: Chemphyschemmentioning

confidence: 99%

See 1 more Smart Citation

Empirical Hydrogen Bonding Donor (HBD) Parameters of Organic Solvents Using Solvatochromic Probes – A Critical Evaluation

Spange

Weiß

2023

ChemPhysChem

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“…At this point, it is worth making a brief comment concerning various quantitative models based on the properties of electron density at the bond critical points, which were previously successfully used for characterization of the energy for various types of noncovalent bonds [ 70 , 71 , 72 , 73 , 74 , 75 ]. Figure S4 shows the correlation between the complexation enthalpy Δ H and G ( r BCP ).…”

Section: Resultsmentioning

confidence: 99%

“…Previously, we have considered a similar but somewhat smaller set of complexes in order to build a correlation between the XB strength/geometry and the changes of two spectral parameters upon complexation: the 31 P NMR chemical shift and the ν(P=O) stretching frequency [ 69 ] (similar correlations for hydrogen-bonded complexes with Me 3 PO were recently published as well [ 70 ]). We have shown that decent correlations of this kind do exist, and they could be fitted by simple analytical functions.…”

Section: Introductionmentioning

confidence: 99%

The Distance between Minima of Electron Density and Electrostatic Potential as a Measure of Halogen Bond Strength

et al. 2022

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In this study, we present results of a detailed topological analysis of electron density (ED) of 145 halogen-bonded complexes formed by various fluorine-, chlorine-, bromine-, and iodine-containing compounds with trimethylphosphine oxide, Me3PO. To characterize the halogen bond (XB) strength, we used the complexation enthalpy, the interatomic distance between oxygen and halogen, as well as the typical set of electron density properties at the bond critical points calculated at B3LYP/jorge-ATZP level of theory. We show for the first time that it is possible to predict the XB strength based on the distance between the minima of ED and molecular electrostatic potential (ESP) along the XB path. The gap between ED and ESP minima exponentially depends on local electronic kinetic energy density at the bond critical point and tends to be a common limiting value for the strongest halogen bond.

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Theory and computation of nuclear shielding

2023

Nuclear Magnetic Resonance

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This chapter continues earlier reviews of essential works on theoretical issues of nuclear magnetic shieldings published from 1 January to 31 December 2022. As previously, the chapter concentrates on theoretical calculations of nuclear shielding parameters and/or chemical shifts in case of free molecules in the gas phase and solution, and in some cases in the solid state using a periodic formulation. The nuclear shieldings in solution are mainly calculated using inexpensive polarizable continuum model of solvent (PCM). The use of discrete solvent molecules (in particular water and other polar solvents), which is essential for correct description of hydrogen bonding, is often omitted by numerous authors. Most calculations use a relatively simple and fast, but reliable density functional theory (DFT) combined with gauge-including atomic orbital (GIAO) approach. On the other hand, reports on prediction of nuclear magnetic shielding parameters using high level theoretical methods combined with large and flexible basis sets are not so common due to the enormous computational cost. In addition, correction of raw theoretical nuclear magnetic shieldings due to ro-vibration (zero-point vibration correction, ZPVC) and temperature corrections (TC), as well as implicit and explicit solvent effects and relativistic corrections are not often reported.

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Phosphine oxides as NMR and IR spectroscopic probes for the estimation of the geometry and energy of PO⋯H–A hydrogen bonds

Abstract: In this work we evaluate the possibility to use the NMR and IR spectral properties of P=O group to estimate the geometry and strength of hydrogen bonds which it forms...

Cited by 6 publications

References 90 publications

Empirical Hydrogen Bonding Donor (HBD) Parameters of Organic Solvents Using Solvatochromic Probes – A Critical Evaluation

Empirical Hydrogen Bonding Donor (HBD) Parameters of Organic Solvents Using Solvatochromic Probes – A Critical Evaluation

The Distance between Minima of Electron Density and Electrostatic Potential as a Measure of Halogen Bond Strength

Theory and computation of nuclear shielding

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