X-ray crystallographic and quantum-chemical investigation of tert-butyl hydroperoxide

Kosnikov, A. Yu.; Antonovskiĭ, V. L.; Lindeman, Sergey V.; Antipin, M. Yu.; Struchkov, Yu. T.; Turovskii, N. A.; Zyat'kov, I. P.

doi:10.1007/bf00580302

Cited by 4 publications

(5 citation statements)

References 8 publications

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“…1). This is consistent with the authors [1], who showed linear correlation between the chemical shifts values in chloroform-d and dimethylsulphoxide-d 6 classes. Equations corresponded to the obtained relationships ( Fig.…”

Section: Experimental Nmr 13 с Spectra Of the 113-trimethyl-3-(4-mesupporting

confidence: 93%

“…Thus, the main attention was focused on the geometry of -CO-OH fragment. The calculation results were compared with known experimental values for the tert-butyl hydroperoxide [6], and appropriate agreement between calculated and experimental parameters can be seen in the case of МР2/6-31G(d,p) method.…”

Section: B U T Y L Hydroperoxide Nmr 13 с Spectra By мр2 and B3lyp Mementioning

confidence: 90%

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. NMR 13C Spectra of the 1,1,3-Trimethyl-3-(4-Methylphenyl)Butyl Hydroperoxide in Various Solvents: Molecular Modeling

Shamne¹,

Raksha²,

Berestneva³

2015

Vestn. Volgogr. gos. univ., Ser. 10. Innov. deiat.

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C chemical shifts as obtained at various computational levels are reported for the 1,1,3-trimethyl-3-(4-methylphenyl)butyl hydroperoxide. The data are compared with experimental solution data in chloroform-d, acetonitrile-d 3 , and DMSO-d 6 , focusing on the agreement with spectral patterns and spectral trends. Calculation of magnetic shielding tensors and chemical shifts for 13 C nuclei of the 1,1,3-trimethyl-3-(4methylphenyl)butyl hydroperoxide molecule in the approximation of an isolated particle and considering the solvent influence in the framework of the continuum polarization model (PCM) was carried out. Comparative analysis of experimental and computer NMR spectroscopy results revealed that the GIAO method with MP2/6-31G(d,p) level of theory and the PCM approach can be used to estimate the NMR 13 C chemical shifts of the 1,1,3-trimethyl-3-(4methylphenyl)butyl hydroperoxide.

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Section: Experimental Nmr 13 с Spectra Of the 113-trimethyl-3-(4-mesupporting

confidence: 93%

Section: B U T Y L Hydroperoxide Nmr 13 с Spectra By мр2 and B3lyp Mementioning

confidence: 90%

. NMR 13C Spectra of the 1,1,3-Trimethyl-3-(4-Methylphenyl)Butyl Hydroperoxide in Various Solvents: Molecular Modeling

Shamne¹,

Raksha²,

Berestneva³

2015

Vestn. Volgogr. gos. univ., Ser. 10. Innov. deiat.

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“…Then the structures reflecting the solvent or TBHP binding with one of the Cr atoms of the building unit were optimized. The results for TBHP are consistent with those obtained in ref. 37 .…”

Section: Computational Detailssupporting

confidence: 92%

“…The results for TBHP are consistent with those obtained in ref. 37. The geometry parameters of substrates are consistent with published data (e.g., ethoxy ethanol (r 40 etc.).…”

Section: Computational Detailssupporting

confidence: 87%

Effect of solvent nature on propylene glycol oxidation with tert-butyl hydroperoxide over metal–organic framework Cr-MIL-101

2019

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“…The SOMO – 1 and SOMO – 2 are nearly degenerate with a separation of 0.037 eV in 2′ ·TBHP, and both are primarily the π*(Ru–Ru) orbitals with significant contribution of p (Cl) lone pair. Similar to the previous study of H 2 O 2 binding to a Ru 2 catalyst, it is likely that the σ-type electron density along the Ru–Ru axial position would be imparted onto TBHP upon its coordination, which leads to a weakened σ(Ru–Ru) and hence more relaxed Ru–Ru bond length, 2.402 Å compared with 2.281 Å in Ru 2 (OAc) 4 Cl·H 2 O. , Meanwhile, coordination to Ru 2 also induced significant changes in the geometry of TBHP: the O–O bond was elongated from 1.473 Å in free TBHP to 1.563 Å, and the H–O1–O2–C dihedral angle relaxed from 104.0° to 135.0°, reflecting the conversion of one of the O1 lone pairs into a dative bonding pair. This result implies the important role of the dative coordination of peroxy species to Ru 2 in the eventual O–O bond cleavage.…”

Section: Resultssupporting

confidence: 68%

tert-Butyl Hydroperoxide Oxygenation of Organic Sulfides Catalyzed by Diruthenium(II,III) Tetracarboxylates

et al. 2013

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Diruthenium(II,III) carboxylates Ru2(esp)2Cl (1a), [Ru2(esp)2(H2O)2]BF4 (1b), and Ru2(OAc)4Cl (2) efficiently catalyze the oxygenation of organic sulfides. As noted in a previous work, 1a is active in oxygenation of organic sulfides with tert-butyl hydroperoxide (TBHP) in CH3CN. Reported herein in detail is the oxygenation activity of 1a, 1b, and 2, with the latter being highly selective in oxo-transfer to organic sulfides using TBHP under ambient conditions. Solvent-free oxidation reactions were achieved through dissolving 1a or 1b directly into the substrate with 2 equiv of TBHP, yielding TOF up to 2056 h(-1) with 1b. Also examined are the rate dependence on both catalyst and oxidant concentration for reactions with catalysts 1a and 2. Ru2(OAc)4Cl may be kinetically saturated with TBHP; however, Ru2(esp)2Cl does not display saturation kinetics. By use of a series of para-substituted thioanisoles, linear free-energy relationships were established for both 1a and 2, where the reactivity constants (ρ) are negative and that of 1a is about half that of 2. Given these reactivity data, two plausible reaction pathways were suggested. Density functional theory (DFT) calculation for the model compound Ru2(OAc)4Cl·TBHP, with TBHP on the open axial site, revealed elongation of the O-O bond of TBHP upon coordination.

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X-ray crystallographic and quantum-chemical investigation of tert-butyl hydroperoxide

Cited by 4 publications

References 8 publications

. NMR 13C Spectra of the 1,1,3-Trimethyl-3-(4-Methylphenyl)Butyl Hydroperoxide in Various Solvents: Molecular Modeling

. NMR 13C Spectra of the 1,1,3-Trimethyl-3-(4-Methylphenyl)Butyl Hydroperoxide in Various Solvents: Molecular Modeling

Effect of solvent nature on propylene glycol oxidation with tert-butyl hydroperoxide over metal–organic framework Cr-MIL-101

tert-Butyl Hydroperoxide Oxygenation of Organic Sulfides Catalyzed by Diruthenium(II,III) Tetracarboxylates

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