Gas phase nucleophilic displacement reactions of negative ions with carbonyl compounds

Asubiojo, O. I.; Brauman, John I.

doi:10.1021/ja00508a002

Cited by 142 publications

(42 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Five coordinates SI-S:, (respectively, "sym," "asym," "wag," "rock," and "twist") for bending about the tetravalent carbon were constructed as linear combinations of the six interbond angles, each being orthogonal to the redundacy condition SO, uiz., (10) and the coefficients al-a6 were as given by T~p k e .~~ One of these coordinates, together with the four endocyclic bond-stretching coordinates and a torsional coordinate, describe the six degrees of freedom of the four-membered ring. The remaining coordinates were the three exocyclic bond stretches and the two exocyclic angles involving H,.…”

Section: Vibrational Propertiesmentioning

confidence: 99%

Determination and characterization of a transition structure for water–formaldehyde addition

1983

View full text Add to dashboard Cite

Quantum mechanical calculations of the geometric, energetic, electronic, and vibrational features of a transition structure for gas-phase water-formaldehyde addition (FWlt) are described, and a new transition-structure search algorithm is presented. Basis-set-dependent effects are assessed by comparisons of computed properties obtained from self-consistent field (SCF) molecular orbital (MO) calculations with STo-3G, 4-31G, and 6-31G** basis sets in the absence of electron correlation. The results obtained suggest that STO-3G-level calculations may be sufficiently reliable for the prediction of the transition structure of FWlt and for the transition structures of related carbonyl addition reactions. Moreover, the calculated activation energy for formation of FWlt from water and formaldehyde (-44 kcal mol-') is very similar in all three basis sets. However, the energy of formaldehyde hydration predicted by STO-3G (--45 kcal mol-l) is about three times larger than that predicted by the other two basis sets, with the activation energy for dihydroxymethane dehydration also being too large in STO-3G. Calculated force constants in all three basis sets are generally too large, leading to vibrational frequencies that are also too large. However, uniformly scaled force constants (in internal coordinates) give much better agreement with experimental frequencies, scaled 4-31G force constants being slightly superior to scaled STO-3G force constants.

show abstract

Section: Vibrational Propertiesmentioning

confidence: 99%

Determination and characterization of a transition structure for water–formaldehyde addition

1983

View full text Add to dashboard Cite

show abstract

“…Afterward, many organic chemists have continued this work [10][11][12][13]. Up to now, numerous experimental kinetic and theoretical researches have studied the mechanism of these reactions [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31].…”

Section: Introductionmentioning

confidence: 99%

Influence of a β-OH substituent on SN2 reactions of fluoroethane: Intramolecular hydrogen bonding catalysis or inhibition? A theoretical study

Ahmadi

Fattahi

2015

Computational and Theoretical Chemistry

View full text Add to dashboard Cite

“…In the gas phase, the addition–elimination reaction has been studied extensively. Most of the researchers investigated reactions of inorganic anions such as hydroxyl anion with carbonyl compounds and focused on the formation of a tetrahedral transition state, similar to the condense phase . There are also few reports about gas phase addition–elimination reaction of aromatic nucleophiles with carbonyl compounds.…”

Section: Introductionmentioning

confidence: 99%

Addition–elimination versus Tishchenko reaction in the gas phase

2014

View full text Add to dashboard Cite

Gas phase reactions of the substituted phenide ions with methyl formate have been studied. It was found that the results of these reactions depend mainly on the basicity of the phenide ion, which is related to the presence of the electron-accepting or electron-donating substituents in the benzene ring. It was shown that the phenide ions substituted with electron-withdrawing groups react with methyl formate in the gas phase in a two-step reaction. The first step that proceeds according to the typical addition-elimination mechanism results in the formation of the anion of the respective benzaldehyde derivative with the negative charge located either in the aldehyde group (acyl anion) or in the benzene ring (phenide anion) in position ortho to an aldehyde moiety. In the second step, the preliminary-formed anion reacts with the second molecule of methyl formate yielding formally product of the second addition-elimination reaction. Theoretical calculations as well as collision induced dissociation spectra of the model compounds suggest that this reaction proceeds according to the Tishchenko reaction mechanism yielding the respective phthalide anion. According to our knowledge, this is the first example of the Tishchenko-type reaction in the gas phase.

show abstract

Gas phase nucleophilic displacement reactions of negative ions with carbonyl compounds

Cited by 142 publications

References 5 publications

Determination and characterization of a transition structure for water–formaldehyde addition

Determination and characterization of a transition structure for water–formaldehyde addition

Influence of a β-OH substituent on SN2 reactions of fluoroethane: Intramolecular hydrogen bonding catalysis or inhibition? A theoretical study

Addition–elimination versus Tishchenko reaction in the gas phase

Contact Info

Product

Resources

About