Reaction of phosphorus pentachloride with N-vinylimidazole and N-vinylbenzimidazole

Ларина, Л. И.; Rozinov, V. G.; Rudyakova, E. V.; Savosik, V. A.; Levkovskaya, G. G.; Dmitrichenko, M. Yu.; Bidusenko, Ivan A.

doi:10.1134/s1070363210020350

Cited by 7 publications

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“…The conditions of synthesis and physicochemical parameters of compounds I-IV were reported in [5,6].…”

Section: Methodsmentioning

confidence: 99%

“…On the other hand, the presence in the heterorings of I and II of pyridine-type nitrogen atoms possessing enhanced nucleophilicity suggests that attack by phosphorus pentachloride can be directed at the heteroring with formation of the corresponding donor-acceptor molecular complexes III and IV [5,6] (Scheme 1) rather than at the side-chain double bond. The 31 P NMR spectra of III and IV contained a singlet in the region δ P -258 to -296 ppm, which is typical of six-coordinate phosphorus atom.…”

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confidence: 97%

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Quantum-chemical calculations of NMR chemical shifts of organic molecules: IV. Effect of intermolecular coordination on 31P NMR shielding constants and chemical shifts of molecular complexes of phosphorus pentachloride with azoles

et al. 2011

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Intermolecular coordination effects on the 31 P NMR spectra of molecular complexes of N-vinylimidazole and 1-allyl-3,5-dimethylpyrazole with phosphorus pentachloride were studied by theoretical and experimental methods. The formation of intermolecular dative N→P bond was shown to be accompanied by upfield shift of the phosphorus resonance signal by more than 200 ppm. Appreciable contribution of relativistic effects to 31 P NMR chemical shifts was revealed; the spin-orbital contribution to 31 P shielding constant was estimated at >210 ppm. Consideration of solvent effect was found to be crucial while studying steric structure of molecular complexes of azoles with phosphorus pentachloride and intermolecular coordination effects on 31 P NMR chemical shifts. * For communication III, see [1].We previously studied by theoretical methods the effect of intramolecular coordination on 31 P NMR shielding constants (chemical shifts) of [2-(1H-pyrazol-1-yl)ethenyl]phosphonium hexachlorophosphate(V) and 1,1,1,1-tetrachloro-1H-1λ 5 -pyrazolo[1,2-a][1,2,3]-diazaphosphol-8-ium-1-ide [1]. While developing our studies on theoretical calculations of 31 P chemical shifts [1][2][3], in the present work we examined molecular complexes of phosphorus pentachloride with some azoles, N-vinylimidazole (I) and 1-allyl-3,5-dimethylpyrazole (II). In keeping with the results of our experimental [4] and theoretical studies [1], the phosphorus atom in chlorophosphonium group is capable of forming a dative bond with pyridine-type nitrogen atom (i.e., sp 2 -nitrogen atom possessing an unshared electron pair). As a result, the coordination number of phosphorus increases to 5 or 6, and its resonance signal in the 31 P NMR spectrum is displaced upfield; therefore, 31 P NMR spectroscopy can be used to analyze structure of such intramolecular complexes.On the other hand, the presence in the heterorings of I and II of pyridine-type nitrogen atoms possessing enhanced nucleophilicity suggests that attack by phosphorus pentachloride can be directed at the heteroring with formation of the corresponding donor-acceptor molecular complexes III and IV [5, 6] (Scheme 1) rather than at the side-chain double bond. The 31 P NMR spectra of III and IV contained a singlet in the region δ P -258 to -296 ppm, which is typical of six-coordinate phosphorus atom. With a view to estimate the effect of intermolecular coordination on the 31 P shielding constants (chemical shifts) and prove the formation of dative bond in molecular complexes III and IV, we performed quantum-chemical calculations of 31 P NMR chemical shifts for the gas phase and with account taken of solvent effect (see table).The phosphorus shielding constants were calculated at the GIAO-B3LYP/DZP level of theory with account

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“…The conditions of synthesis and physicochemical parameters of compounds I-IV were reported in [5,6].…”

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 97%

Quantum-chemical calculations of NMR chemical shifts of organic molecules: IV. Effect of intermolecular coordination on 31P NMR shielding constants and chemical shifts of molecular complexes of phosphorus pentachloride with azoles

et al. 2011

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“…2‐(1‐Pytazolyl)ethenyltrichlorophosphonium hexachlorophosphorate ( 1 ) and 2‐(1‐pyrozolyl)ethenyltetrachlorophosphonium ( 2 ) were synthesised via the phosphorylation of N ‐vinylpyrazole with phosphorous pentachloride, 6 whereas intermolecular complexes of N ‐vinylimidazole and 1‐allyl‐3,5‐dimethilpyrazole with phosphorous pentachloride, accordingly 3 and 4 , were obtained as described elsewhere . All products under study obtained in this way (compounds 1–4 ) were identified according to the published NMR data …”

Section: Methodsmentioning

confidence: 99%

The effects of intramolecular and intermolecular coordination on ³¹P nuclear shielding: phosphorylated azoles

Chernyshev

Ларина²,

Chirkina³

et al. 2012

Magnetic Reson in Chemistry

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The effects of intramolecular and intermolecular coordination on (31)P nuclear shielding have been investigated in the series of tetracoordinated, pentacoordinated and hexacoordinated N-vinylpyrazoles and intermolecular complexes of N-vinylimidazole and 1-allyl-3,5-dimethylpyrazole with phosphorous pentachloride both experimentally and theoretically. It was shown that either intramolecular or intermolecular coordination involving phosphorous results in a dramatic (31)P nuclear shielding amounting to approximately 150 ppm on changing the phosphorous coordination number by one. A major importance of solvent effects on (31)P nuclear shielding of intramolecular and intermolecular complexes involving N → P coordination bond has been demonstrated. It was found that the zeroth-order regular approximation-gauge-including atomic orbital-B1PW91/DZP method was sufficiently accurate for the calculation of (31)P NMR chemical shifts, provided relativistic corrections are taken into account, the latter being of crucial importance in the description of (31)P nuclear shielding.

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“…Establishing the structure of the compounds using nuclear quadrupole spectroscopy 35 Cl and the assignment of signals in the experimental spectra without attracting quantum chemical calculations in many cases quite is difficult. 35 Cl NQR frequencies at 77 K (ν, MHz) and signal-to noise ratio (s/n) in the spectra of chloro-containing 1,2,4-triazoles (1-6) and imidazoles (7)(8)(9)(10)(11)(12).…”

Section: Chlorinated Five-membered Azolesmentioning

confidence: 99%

“…The35 Cl NQR frequencies at 77 K (ν, MHz) and signal-to noise ratio (s/n) in the spectra of chloro-containing 1,2,4-triazoles (1-6) and imidazoles(7)(8)(9)(10)(11)(12).…”

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Nuclear Quadrupole Resonance Spectroscopy: Tautomerism and Structure of Functional Azoles

Ларина

2019

Crystals

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The Nuclear Quadrupole Resonance spectroscopy data of functionalized azoles (imidazoles, triazoles and corresponding benzazoles) are reviewed and critically discussed. The possibility of studying the tautomerism of azoles by the NQR method is considered.Crystals 2019, 9, 366 2 of 12 transfer of a chlorine atom between 1-chlorobenzimidazole and benzimidazole in a CCl 4 /CH 3 OH/K 2 CO 3 medium [52,53]. A similar chlorotropic rearrangement was observed in the equilibrium exchange process between 1-chloroindole and 3-chloro-3H-indole, i.e., the fast intermolecular transformations of 1-chloroindole to 3-chloroindole in the related media were detected [53]. The base-promoted intermolecular mechanism rationalizes chlorotropic processes in N-chlorosubstituted azoles. NQR spectroscopy data are missing.X-ray single-crystal analysis of 1,2,4-triazole (Scheme 1) have revealed a crystalline state of the asymmetric 1H(2H)-tautomer (A, C) [54,55]. Quantum-chemical (ab initio) calculations of 1,2,4-triazole tautomers suggest the prevailing of 1H(2H)-1,2,4-triazole in gas phase as compared to 4H-1,2,4-tautomer by~7 kcal/mol [56][57][58][59], that agrees with experimental data [60,61].

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Reaction of phosphorus pentachloride with N-vinylimidazole and N-vinylbenzimidazole

Cited by 7 publications

References 1 publication

Quantum-chemical calculations of NMR chemical shifts of organic molecules: IV. Effect of intermolecular coordination on 31P NMR shielding constants and chemical shifts of molecular complexes of phosphorus pentachloride with azoles

Quantum-chemical calculations of NMR chemical shifts of organic molecules: IV. Effect of intermolecular coordination on 31P NMR shielding constants and chemical shifts of molecular complexes of phosphorus pentachloride with azoles

The effects of intramolecular and intermolecular coordination on ³¹P nuclear shielding: phosphorylated azoles

Nuclear Quadrupole Resonance Spectroscopy: Tautomerism and Structure of Functional Azoles

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Reaction of phosphorus pentachloride with N-vinylimidazole and N-vinylbenzimidazole

Cited by 7 publications

References 1 publication

Quantum-chemical calculations of NMR chemical shifts of organic molecules: IV. Effect of intermolecular coordination on 31P NMR shielding constants and chemical shifts of molecular complexes of phosphorus pentachloride with azoles

Quantum-chemical calculations of NMR chemical shifts of organic molecules: IV. Effect of intermolecular coordination on 31P NMR shielding constants and chemical shifts of molecular complexes of phosphorus pentachloride with azoles

The effects of intramolecular and intermolecular coordination on 31P nuclear shielding: phosphorylated azoles

Nuclear Quadrupole Resonance Spectroscopy: Tautomerism and Structure of Functional Azoles

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The effects of intramolecular and intermolecular coordination on ³¹P nuclear shielding: phosphorylated azoles