Quantum-chemical calculations of chemical shifts in NMR spectra of organic molecules: V. Stereochemical structure of unsaturated phosphonic acids dichlorides from 31P NMR spectral data

Chernyshev, K. A.; Ларина, Л. И.; Chirkina, E. A.; Rozinov, V. G.; Krivdin, Leonid B.

doi:10.1134/s1070428012050077

Cited by 14 publications

(8 citation statements)

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“…[37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55] In several systematic studies it was shown 48-55 that a satisfactory agreement between calculations and experiments is observed when quite a ''heavy'' basis set or high level of theory ‡ was used although deviations and exceptions were also found. In fact, there are relatively few reports on 31 P NMR CS calculations using quantum chemical methods.…”

Section: Introductionmentioning

confidence: 99%

“…In fact, there are relatively few reports on 31 P NMR CS calculations using quantum chemical methods. [37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55] In several systematic studies it was shown [48][49][50][51][52][53][54][55] that a satisfactory agreement between calculations and experiments is observed when quite a ''heavy'' basis set or high level of theory ‡ was used although deviations and exceptions were also found. It is necessary to stress that all these studies were focused only on the restricted types of small size compounds.…”

Section: Introductionmentioning

confidence: 99%

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Quantum chemical calculations of³¹P NMR chemical shifts: scopes and limitations

Latypov

Polyancev

Yakhvarov

et al. 2015

Phys. Chem. Chem. Phys.

122

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The aim of this work is to convince practitioners of (31)P NMR methods to regard simple GIAO quantum chemical calculations as a safe tool in structural analysis of organophosphorus compounds. A comparative analysis of calculated GIAO versus experimental (31)P NMR chemical shifts (CSs) for a wide range of phosphorus containing model compounds was carried out. A variety of combinations (at the HF, DFT (B3LYP and PBE1PBE), and MP2 levels using 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) basis sets) were tested. On the whole, it is shown that, in contrast to what is claimed in the literature, high level of theory is not needed to obtain rather accurate predictions of (31)P CSs by the GIAO method. The PBE1PBE/6-31G(d)//PBE1PBE/6-31G(d) level can be recommended for express estimation of (31)P CSs. The PBE1PBE/6-31G(2d)//PBE1PBE/6-31G(d) combination can be recommended for routine applications. The PBE1PBE/6-311G(2d,2p)//PBE1PBE/6-31+G(d) level can be proposed to obtain better results at a reasonable cost. Scaling by linear regression parameters significantly improves results. The results obtained using these combinations were demonstrated in (31)P CS calculations for a variety of medium (large) size organic compounds of practical interest. Care has to be taken for compounds that may be involved in exchange between different structural forms (self-associates, associates with solvent, tautomers, and conformers). For phosphorus located near the atoms of third period elements ((CH3)3PS and P(SCH3)3) the impact of relativistic effects may be notable.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Quantum chemical calculations of³¹P NMR chemical shifts: scopes and limitations

Latypov

Polyancev

Yakhvarov

et al. 2015

Phys. Chem. Chem. Phys.

122

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“…Thus, the reactions of trichloro(2 ethoxyethenyl) phosphonium and trichloro(styryl)phosphonium hexa chlorophosphorates with triethylamine were studied by 1 Н, 13 С, and 31 Р NMR spectroscopy. It was shown that the primary reaction products are phosphonyl chlorides.…”

Section: Methodsmentioning

confidence: 99%

NMR study of reactions of organyltrichlorophosphonium hexachlorophosphorates with triethylamine

2015

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The reactions of trichloro(2 ethoxyethenyl)phosphonium and trichloro(styryl)phosphonium hexachlorophosphorates with triethylamine were studied by 1 Н, 13 С, and 31 Р NMR spectro scopy. It was shown that phosphonyl chlorides are the primary products of the reactions. The presence of the alkoxy group in hexachlorophosphorate results in the oxidation of the PCl 2 group to form phosphonyl chlorides. Diphosphorylated oxaphosphinines were synthesized.Chemistry of unsaturated organophosphorus com pounds is among vigorously developed sections of organo phosphorus chemistry. Interest in unsaturated organo phosphorus compounds is caused by their significance for synthetic chemistry of macromolecular materials, complexones, extragents, antipyrenes, drugs, and phos phorus containing pesticides. 1-3 Earlier we studied the phosphorylation of unsaturated compounds, N vinylazoles and their derivatives, and other organic nucleophiles by phosphorus pentachloride derivatives. 4-17 In particular, it was shown that many N vinylazoles react with phos phorus pentachloride to form unsaturated organophos phorus compounds containing tetra , penta , and hexa coordinated phosphorus atoms. 4,9-12,16,17 The phos phorylation of tertiary amines containing at least two ethyl groups at the nitrogen atom by phosphorus pentachloride affords new C chlorophosphorylated enamines. 5 At the same time, the presence in the amine molecule of two aryl substituents and one ethyl group deactivates the latter, and no phosphorylation occurs. The possibility of substi tution of two chlorine atoms in the PCl 5 molecule by alk enyl groups was demonstrated for N ethyl N methyl aniline. 5 There are no indications in literature to the possibility of using accessible alkenyltrichlorophosphonium hexa chlorophosphorates for the phosphorylation of ethers, di alkenyl sulfides, and tertiary amines. The most abundant * Dedicated to Academician of the Russian Academy of Sciences V. I. Minkin on the occasion of his 80th birthday.

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“…In a continuation of the earlier publications by Chernyshev and coauthors, in the paper, the molecule of phosphine, PH 3 , was taken as a reference with a value of phosphorus shielding constant of 606.11 ppm, as evaluated by Lantto, et al at the CCSD(T)/cc‐pwCV5Z level without taking into account relativistic, rovibrational, and temperature corrections. This nonrelativistic GIAO‐CCSD(T)/cc‐pwCV5Z shielding constant was then corrected by evaluating relativistic contribution at the four‐component Dirac–Coulomb level to give 624.309 ppm and finally rovibrationally and temperature corrected to give the final value of 614.758 ppm.…”

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 of chemical shifts in NMR spectra of organic molecules: V. Stereochemical structure of unsaturated phosphonic acids dichlorides from 31P NMR spectral data

Cited by 14 publications

References 10 publications

Quantum chemical calculations of³¹P NMR chemical shifts: scopes and limitations

Quantum chemical calculations of³¹P NMR chemical shifts: scopes and limitations

NMR study of reactions of organyltrichlorophosphonium hexachlorophosphorates with triethylamine

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

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Quantum-chemical calculations of chemical shifts in NMR spectra of organic molecules: V. Stereochemical structure of unsaturated phosphonic acids dichlorides from 31P NMR spectral data

Cited by 14 publications

References 10 publications

Quantum chemical calculations of31P NMR chemical shifts: scopes and limitations

Quantum chemical calculations of31P NMR chemical shifts: scopes and limitations

NMR study of reactions of organyltrichlorophosphonium hexachlorophosphorates with triethylamine

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

Contact Info

Product

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Quantum chemical calculations of³¹P NMR chemical shifts: scopes and limitations

Quantum chemical calculations of³¹P NMR chemical shifts: scopes and limitations

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