Van der Waals complexes in 1,3-dipolar cycloaddition reactions: ozone-ethylene

Gillies, C. W.; Gillies, J. Z.; Suenram, R. D.; Lovas, Francis J.; Kraka, Elfi; Cremer, Dieter

doi:10.1021/ja00007a010

Cited by 98 publications

(89 citation statements)

References 2 publications

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“…All three organics have electron-rich π systems, and the formation of weak π complexes between ozone and alkenes has been reported at low temperatures, [62][63][64] suggesting that perhaps partial electron transfer is a key step in the oxidation.…”

Section: Resultsmentioning

confidence: 99%

“…Four angstroms was selected as the cutoff distance based on ab initio calculations suggesting that a stable complex is formed on the reaction pathway at a separation of 3.291 Å. 64 The rates obtained for O 3 collision with the surface are slower than its collision rates with the terminal alkene by factors of 8 and 12 for C3d and C8d, respectively (Table 1). This apparent difference between collision rates of O 3 with the surface and with alkene groups is due to inelastic collisions of O 3 with the surface, yielding multiple collisions with the terminal alkenes in every collision with the SAM surface.…”

Section: Resultsmentioning

confidence: 99%

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Interaction of Gas-Phase Ozone at 296 K with Unsaturated Self-Assembled Monolayers: A New Look at an Old System

et al. 2004

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The oxidation of organics adsorbed on surfaces by ozone is of fundamental chemical interest and potentially important in the lower atmosphere. Studies of the oxidation of the three-carbon and eight-carbon vinylterminated self-assembled monolayers (SAMs, C3d and C8d) on a silicon ATR (attenuated total reflectance) crystal by gas-phase O 3 at 296 K are reported. Oxidation of the SAMs was followed in real time by ATR-FTIR using ozone concentrations that spanned 5 orders of magnitude, from ∼10 11 to 10 16 molecules cm -3 . For comparison, some studies of the saturated C8 SAM were also carried out. The films were also characterized by atomic force microscopy and water contact angle measurements. The loss of CdC and the formation of CdO were measured in real time and shown to be consistent with a Langmuir-Hinshelwood mechanism in which O 3 is rapidly adsorbed on the surface and then reacts more slowly with the alkene moiety. This is supported by molecular dynamics (MD) calculations which show that O 3 does not simply undergo elastic collisions but has a significant residence time on the surface. However, the kinetics measurements indicate a much longer residence time than the MD calculations, suggesting a chemisorption of O 3 . Formaldehyde was observed as a gas-phase product by infrared cavity ring down spectroscopy. Possible mechanisms of the ozonolysis and its atmospheric implications are discussed.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Interaction of Gas-Phase Ozone at 296 K with Unsaturated Self-Assembled Monolayers: A New Look at an Old System

et al. 2004

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“…The final mycophenolic acid was identical with purchased one (Tocris Bioscience), and we were able to use it in synthesis of the novel analogues of MPA. [34][35][36][37] 1.…”

Section: Resultsmentioning

confidence: 99%

Modifications of total synthesis of mycophenolic acid

Cholewiński¹,

Ugarte²,

Siebert³

et al. 2018

10.5267/j.ccl

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“…In fact, the RMP method has been successfully applied to the locations of various concerted TS [20] and concerted TS1 for the addition of O 3 to ethylene [31]. However, a very large stabilization energy (5.8 kcal mol −1 after zero point correction) was predicted by the RMP2 6-31G(d,p) method because of the instability of the zero-order RHF solution for the complex.…”

Section: Concerted Mechanism Of Ozonolysis Reactionsmentioning

confidence: 99%

“…However, a very large stabilization energy (5.8 kcal mol −1 after zero point correction) was predicted by the RMP2 6-31G(d,p) method because of the instability of the zero-order RHF solution for the complex. The best ab initio calculation predicts that the stabilization energy is in the range of 0.7-1.0 kcal mol −1 [31]. On the other hand, the calculated barrier heights for TS1 after the zero point correction are, respectively, 16.3, 5.5 and 2.5 kcal mol by the RMP2 method is in good agreement with the experimental estimation of 5 kcal mol −1 , since the instability of RHF is decreased at TS1.…”

Section: Concerted Mechanism Of Ozonolysis Reactionsmentioning

confidence: 99%

Theoretical study on electronic structures of oxygenated dipoles and mechanisms of ozonolysis reactions

Yoshioka

Yamaki

Kubo

et al. 1997

Elect J Theoret Chem

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SUMMARYThe different orbitals for different spins molecular orbital and complete active space SCF studies of ozone and carbonyl oxide and related ozonolysis reactions were carried out. The RHF, UHF, approximately spin-projected (AP) UHF and CASSCF calculations were performed to elucidate the covalent bond instability of the oxygenated dipoles. The correlation energies were calculated by RMP4, UMP4, APUMP4 and CASPT2 methods. The locations of concerted transition structures for ozonolysis reactions and the full geometry optimizations of 1,5 biradicals formed by the O-O cleavage of first ozonide were carried out. The implications of these results are discussed in relation to concerted and biradical mechanisms of 1,3-dipolar additions and ozonolyses in gas phases.

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Van der Waals complexes in 1,3-dipolar cycloaddition reactions: ozone-ethylene

Cited by 98 publications

References 2 publications

Interaction of Gas-Phase Ozone at 296 K with Unsaturated Self-Assembled Monolayers: A New Look at an Old System

Interaction of Gas-Phase Ozone at 296 K with Unsaturated Self-Assembled Monolayers: A New Look at an Old System

Modifications of total synthesis of mycophenolic acid

Theoretical study on electronic structures of oxygenated dipoles and mechanisms of ozonolysis reactions

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