Quantum chemical calculations of<sup>31</sup>P NMR chemical shifts: scopes and limitations

Latypov, Shamil K.; Polyancev, Fedor M.; Yakhvarov, Dmitry G.; Sinyashin, Оleg G.

doi:10.1039/c5cp00240k

Cited by 85 publications

(126 citation statements)

References 99 publications

(153 reference statements)

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“…The accurate determination of NMR parameters is a challenging task and requires simulation of electron correlation and extended basis set. 71 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 employed to derive the NMR parameters in the recent literature [78][79][80][81][82][83][84][85] and accordingly the M05-2x/6-311++G(d,p) approach has been identified to be economical and convenient in terms of quality to cost ratio for obtaining the NMR chemical shifts. We therefore employ this level of theory for deriving NMR characteristics of aromatic AAILs studied in this work.…”

Section: H and 13 C Nmrmentioning

confidence: 99%

Electronic Structure, NMR, Spin–Spin Coupling, and Noncovalent Interactions in Aromatic Amino Acid Based Ionic Liquids

Rao

Gejji

2016

J. Phys. Chem. A

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Noncovalent interactions accompanying phenylalanine (Phe), tryptophan (Trp), and tyrosine (Tyr) amino acids based ionic liquids (AAILs) composed of 1-methyl-3-butyl-imidazole and its methyl-substituted derivative as cations have been analyzed employing the dispersion corrected density functional theory. It has been shown that cation-anion binding in these bioionic ILs is primarily facilitated through hydrogen bonding in addition to lp---π and CH---π interactions those arising from aromatic moieties which can be probed through (1)H and (13)C NMR spectra calculated from the gauge independent atomic orbital method. Characteristic NMR spin-spin coupling constants across hydrogen bonds of ion pair structures viz., Fermi contact, spin-orbit and spin-dipole terms show strong dependence on mutual orientation of cation with the amino acid anion. The spin-spin coupling mechanism transmits spin polarization via electric field effect originating from lp---π interactions whereas the electron delocalization from lone pair on the carbonyl oxygen to antibonding C-H orbital is facilitated by hydrogen bonding. It has been demonstrated that indirect spin-spin coupling constants across the hydrogen bonds correlate linearly with hydrogen bond distances. The binding energies and dissected nucleus independent chemical shifts (NICS) document mutual reduction of aromaticity of hydrogen bonded ion pairs consequent to localization of π-character. Moreover the nature and type of such noncovalent interactions governing the in-plane and out-of-plane NICS components provide a measure of diatropic and paratropic currents for the aromatic rings of varying size in AAILs. Besides the direction of frequency shifts of characteristic C═O and NH stretching vibrations in the calculated vibrational spectra has been rationalized.

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Section: H and 13 C Nmrmentioning

confidence: 99%

Electronic Structure, NMR, Spin–Spin Coupling, and Noncovalent Interactions in Aromatic Amino Acid Based Ionic Liquids

Rao

Gejji

2016

J. Phys. Chem. A

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“…However, phosphorus nucleus is very sensitive to the electronic structure. Latypov et al have illustrated that comparing theoretical gas‐phase CSs with experimental values is trustworthy and authentic . They have considered all the possible contributions to the shielding, which can be written by Equation :

σ = σ_{vacuum} + σ_{dia} + σ_{polar} + σ_{rovibrat} + σ_{solvent effect},

where σ vacuum is the magnetic shielding for an isolated molecule in vacuum, σ dia is the contribution of the bulk diamagnetic susceptibility of the sample, σ polar is the influence of the medium polarity, σ rovibrat is a rovibronic correlation term, and σ solvent effect is the impact of specific solvent effects.…”

Section: Resultsmentioning

confidence: 99%

“…In a nutshell, highest correlations are achieved at BP86/6–31+G*//BP86/6–31+G*, which exemplify that further polarization and diffuse functions are not mandatory to attain accurate isotropic values. Latypov et al also have shown that high levels of theory and/or heavy combinations do not necessarily yield authentic 31 P CSs …”

Section: Resultsmentioning

confidence: 99%

Toward the comprehensive calculations on the relationship between ¹H, ¹³C, ³¹P chemical shifts, ²J_PH, and the bonding structure of different phosphoryl benzamides

Gholivand

Maghsoud

Hosseini

et al. 2019

Magnetic Reson in Chemistry

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A comprehensive investigation was performed on 1H, 13C, and 31P nuclear magnetic resonance (NMR) chemical shifts (CSs) of phosphoryl benzamide derivatives (C6H5C(O)NHP(O)R1R2), (R1, R2 = aziridine [L1], azetidine [L2], pyrrolidine [L3], piperidine [L4], azepane [L5], 4‐methylpiperidine [L6], propane‐2‐amine [L7], and 2‐methylpropane‐2‐amine [L8]) by the gauge‐independent atomic orbital method (GIAO) to find the most accordant level of theory with the experimental values. To achieve this goal, all the structures were optimized using the B3LYP, BP86, PBE1PBE, M06‐2X, MPWB1K, and MP2 methods with 6–31+G* basis set. Computed structural parameters demonstrate that BP86 has the best agreement to the experimental values between the other methods. The def2‐TZVP and aug‐cc‐pVDZ basis sets were also employed to inspect the effect of different types of basis sets with higher polarization and diffuse functions. The correlation between the empirical and computational values attests that 6–31+G* basis set is the optimum case regarding minimization of the costs and results. The comparison between calculated and experimental CSs at all mentioned combinations illustrated that in accordance with structural results, the best level of theory in CSs is also BP86/6–31+G*. Besides, 2JPH values were computed with an acceptable agreement to experimental data at the optimum level of theory. The dependency between 2JPH and the bonding structure of studied ligands was also scrutinized by the Natural Bond Orbital (NBO) analysis that interprets the relationship between the electronic properties and 2JPH values.

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“…Latypov, et al in continuation of their earlier studies performed a series of DFT, HF, and MP2 calculations of 31 P NMR chemical shifts using a family of Pople's basis sets 6‐31G(d), 6‐31 + G(d), 6‐31G(2d), 6‐31G(d,p), 6‐31 + G(d,p), 6‐311G(d), 6‐311G(2d,2p), 6‐311++G(d,p), 6‐311++G(2d,2p), and 6‐311++G(3df,3pd) in a wide series of phosphorus‐containing compounds of different types 1 – 34 shown in Scheme . On the whole, it was demonstrated that the higher level of theory was not needed to obtain accurate predictions of 31 P NMR chemical shifts.…”

Section: Computation Of 31p Nmr Chemical Shifts: Accuracy Factors Andmentioning

confidence: 99%

Recent advances in computational ³¹P NMR: Part 1. Chemical shifts

Krivdin

2019

Magnetic Reson in Chemistry

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This is the first part of two closely related reviews dealing with the computation of phosphorus-31 nuclear magnetic resonance chemical shifts in a wide series of organophosphorus compounds including complexes, clusters, and bioorganic phosphorus compounds. In particular, the analysis of the accuracy factors, such as substitution effects, solvent effects, vibrational corrections, and relativistic effects, is presented. This review is dedicated to the Full Member of the Russian Academy of Sciences Professor Boris A. Trofimov in view of his invaluable contribution to the field of synthesis, nuclear magnetic resonance, and computation studies of organophosphorus compounds. KEYWORDS computational P-31 NMR, P-31 chemical shiftsThis review is dedicated to the Full Member of the Russian Academy of Sciences Professor Boris A. Trofimov in view of his invaluable contribution to the field of synthesis, NMR investigation, and computational studies of organophosphorus compounds. He is the author of 43 books and chapters in books, some 70 reviews, about 1,500 research papers and has been a scientific supervisor for approximately 90 Ph.D. and 30 D.Sc. dissertations. The apogee of his creativity and scientific achievements is a fundamental book "The Chemistry

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Quantum chemical calculations of³¹P NMR chemical shifts: scopes and limitations

Cited by 85 publications

References 99 publications

Electronic Structure, NMR, Spin–Spin Coupling, and Noncovalent Interactions in Aromatic Amino Acid Based Ionic Liquids

Electronic Structure, NMR, Spin–Spin Coupling, and Noncovalent Interactions in Aromatic Amino Acid Based Ionic Liquids

Toward the comprehensive calculations on the relationship between ¹H, ¹³C, ³¹P chemical shifts, ²J_PH, and the bonding structure of different phosphoryl benzamides

Recent advances in computational ³¹P NMR: Part 1. Chemical shifts

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Quantum chemical calculations of31P NMR chemical shifts: scopes and limitations

Cited by 85 publications

References 99 publications

Electronic Structure, NMR, Spin–Spin Coupling, and Noncovalent Interactions in Aromatic Amino Acid Based Ionic Liquids

Electronic Structure, NMR, Spin–Spin Coupling, and Noncovalent Interactions in Aromatic Amino Acid Based Ionic Liquids

Toward the comprehensive calculations on the relationship between 1H, 13C, 31P chemical shifts, 2JPH, and the bonding structure of different phosphoryl benzamides

Recent advances in computational 31P NMR: Part 1. Chemical shifts

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Quantum chemical calculations of³¹P NMR chemical shifts: scopes and limitations

Toward the comprehensive calculations on the relationship between ¹H, ¹³C, ³¹P chemical shifts, ²J_PH, and the bonding structure of different phosphoryl benzamides

Recent advances in computational ³¹P NMR: Part 1. Chemical shifts