Thermochemistry of strained-ring bridgehead nitriles and esters

Baldt, J. H.; Hall, H.

doi:10.1021/ja00730a025

Cited by 82 publications

(7 citation statements)

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“…The computed density value reported by Nikitin and Lyubartsev based on their new model was 0.773 g·cm −3 with the low deviation of about ∼0.3–0.6% from the available experimental values . A similar improvement was reproduced in the computed molar enthalpy of vaporization, 33.51 kJ·mol −1 , with the low deviation of about ∼0.03–3% from the experimental values …”

Section: Introductionsupporting

confidence: 61%

“…By considering different simulation details, Grabuleda et al achieved simulated thermodynamic properties such as density (from 0.712 to 0.758 g·cm −3 ) and molar enthalpy of vaporization (from 7.33 to 8.46 kcal·mol −1 ) with the relative errors of δρ ∼ 2.44–8.36% and

δ Δ H_{m}^{v a p}

∼ 5.62–8.49% compared to the experimental ones ( ρ exp = 0.777 g·cm −3 ;

Δ H_{m}^{v a p}_{(\exp)}

= 33.5138 kJ·mol −1 ). The ability of the model proposed by Grabuleda et al is not tested in the prediction of dynamical and transport properties of ACN in the original work.…”

Section: Introductionmentioning

confidence: 99%

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Systematic evaluation and refinement of existing all‐atom force fields for the simulation of liquid acetonitrile

Kowsari

Tohidifar

2018

J Comput Chem

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The reliability of a molecular dynamics (MD) simulation study mainly depends on the accuracy of the applied force field. Unlike the ability of some potential models for reasonably predicting the thermodynamic properties of acetonitrile (ACN), simulated dynamical properties such as self-diffusion are generally underestimated compared to experimental values. The present work focuses on the evaluation and refinement of several available all-atom force fields for ACN and proposes a refined flexible six-site potential model. The main modification is related to the reduction of intermolecular LJ parameters (σ and ɛ) for hydrogen atoms, especially ɛ, significantly affecting the dynamical behavior. Besides, the adjustment of σ and ɛ for nitrile carbon and nitrogen atoms helps reach optimum results. Our refined model shows an excellent agreement with the experiment for self-diffusion coefficient and thermodynamic quantities as well as providing a qualitative description of the microscopic structure of liquid ACN. © 2018 Wiley Periodicals, Inc.

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Section: Introductionsupporting

confidence: 61%

δ Δ H_{m}^{v a p}

∼ 5.62–8.49% compared to the experimental ones ( ρ exp = 0.777 g·cm −3 ;

Δ H_{m}^{v a p}_{(\exp)}

= 33.5138 kJ·mol −1 ). The ability of the model proposed by Grabuleda et al is not tested in the prediction of dynamical and transport properties of ACN in the original work.…”

Section: Introductionmentioning

confidence: 99%

Systematic evaluation and refinement of existing all‐atom force fields for the simulation of liquid acetonitrile

Kowsari

Tohidifar

2018

J Comput Chem

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“…There are at least four experimental values [36][37][38][39] for the formation enthalpy of methyl formate that range from -336.9 to -362.3 kJ mol -1 ; if we compare the reaction enthalpies for channels 1-3 based on each of the four experimental values with our ab initio computed heats of reaction, Table 1, then the Gladii et al 36 and Guthrie 37 results can be ruled out. An average of the Hine and Klueppet 38 and the Baldt and Hall 39 values is in good agreement with our computed value of -359.4 ( 4.1 kJ mol -1 for the Z-rotamer of methyl formate. In turn this agrees with computations by Sumathi and Green.…”

Section: Resultsmentioning

confidence: 99%

Ab Initio Chemical Kinetics of Methyl Formate Decomposition: The Simplest Model Biodiesel

2010

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The energetics and kinetics of methyl formate decomposition have been investigated by high-level ab initio calculations with rate constant predictions. The paucity of reliable experimental data for methyl formate has been circumvented by studying a very similar system, namely, the decarboxylation of acetic acid, in order to help validate the theoretical calculations. Our study shows that methyl formate decomposes to methanol and carbon monoxide, almost exclusively, with a high pressure limit rate constant of k(1)(infinity) = 2.128 x 10(12)T(0.735) exp(-34,535/T) s(-1), and the decomposition of acetic acid to methane and carbon dioxide proceeds with a rate constant, k(4)(infinity), of 1.668 x 10(10)T(1.079) exp -35,541/T s(-1). Experimental values for the formation enthalpy of methyl formate are discussed, and it is shown that these can be reconciled with our computed value for DeltaH(f) (298.15 K) of -360.1 +/- 2.2 kJ mol(-1). In turn, bond dissociation energies for all single bonds in the molecule are presented.

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“…This transfer-hydrogenation process most likely involves palladium hydride chemistry, without involvement of "free" H 2 , as methanol dehydrogenation to H 2 and DMC, MF or CO is endothermic by about + 21, + 48 and + 44 kcal mol À1 , respectively. [65][66][67] First, Pd-hydride formation might take place by oxidative addition of methanol to P 2 Pd 0 to give C2b/c, as shown at the bottom of Scheme 5. Displacement of a CH 3 O À anion by nitrobenzene gives cationic Pd hydride C3b/c.…”

Section: Discussionmentioning

confidence: 99%

Carbonylation of Nitrobenzene in Methanol with Palladium Bidentate Phosphane Complexes: An Unexpectedly Complex Network of Catalytic Reactions, Centred around a Pd–imido Intermediate

Mooibroek

Schoon

Bouwman

et al. 2011

Chemistry A European J

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The reactivity of palladium complexes of bidentate diaryl phosphane ligands (P(2)) was studied in the reaction of nitrobenzene with CO in methanol. Careful analysis of the reaction mixtures revealed that, besides the frequently reported reduction products of nitrobenzene [methyl phenyl carbamate (MPC), N,N'-diphenylurea (DPU), aniline, azobenzene (Azo) and azoxybenzene (Azoxy)], large quantities of oxidation products of methanol were co-produced (dimethyl carbonate (DMC), dimethyl oxalate (DMO), methyl formate (MF), H(2)O, and CO). From these observations, it is concluded that several catalytic processes operate simultaneously, and are coupled via common catalytic intermediates. Starting from a P(2)Pd(0) compound formed in situ, oxidation to a palladium imido compound P(2)Pd(II)=NPh, can be achieved by de-oxygenation of nitrobenzene 1) with two molecules of CO, 2) with two molecules of CO and the acidic protons of two methanol molecules, or 3) with all four hydrogen atoms of one methanol molecule. Reduction of P(2)Pd(II)=NPh to P(2)Pd(0) makes the overall process catalytic, while at the same time forming Azo(xy), MPC, DPU and aniline. It is proposed that the Pd-imido species is the central key intermediate that can link together all reduction products of nitrobenzene and all oxidation products of methanol in one unified mechanistic scheme. The relative occurrence of the various catalytic processes is shown to be dependent on the characteristics of the catalysts, as imposed by the ligand structure.

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Thermochemistry of strained-ring bridgehead nitriles and esters

Cited by 82 publications

References 0 publications

Systematic evaluation and refinement of existing all‐atom force fields for the simulation of liquid acetonitrile

Systematic evaluation and refinement of existing all‐atom force fields for the simulation of liquid acetonitrile

Ab Initio Chemical Kinetics of Methyl Formate Decomposition: The Simplest Model Biodiesel

Carbonylation of Nitrobenzene in Methanol with Palladium Bidentate Phosphane Complexes: An Unexpectedly Complex Network of Catalytic Reactions, Centred around a Pd–imido Intermediate

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