Solvent and secondary kinetic isotope effects for the microhydrated SN2 reaction of Cl-(H2O)n with CH3Cl

Zhao, Xuhao; Tucker, Susan C.; Truhlar, Donald G.

doi:10.1021/ja00003a015

Cited by 140 publications

(89 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Simple S N 2 reactions, such as the focus reaction of this study, are some of the most fundamental reactions in organic chemistry and have provided keen insights into gas phase reactivity and aqueous, solvation properties, reaction energetics, and kinetics over the past several decades. [13][14][15][16][17] It is well known that S N 2 reactions, when in the gas phase, have an double-well potential energy surface with a single transition state (TS), as seen in Figure 1, bracketed on either side by low wells generated from the formation of a more energetically stable Ion-Dipole Complex (IDC). Then, when the reaction is moved into solution, the reaction profile is likely to be dominated by an enhanced central barrier.…”

Section: Introductionmentioning

confidence: 99%

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl− attack on CH3Cl

Kuechler

York

2014

The Journal of Chemical Physics

View full text Add to dashboard Cite

The nucleophilic attack of a chloride ion on methyl chloride is an important prototype S N 2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resulting free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models. © 2014 AIP Publishing LLC. [http://dx

show abstract

Section: Introductionmentioning

confidence: 99%

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl− attack on CH3Cl

Kuechler

York

2014

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…The first indication that the origin of these KIEs was more complicated than the simple theory suggested, came from theoretical calculations by Williams, 26 by Truhlar and coworkers 27,28 and by Wolfe and Kim. 29 All these workers reported that the major contribution to the secondary a-deuterium KIE in S N 2 reactions was due to the C a -H(D) stretching vibrations rather than the C a -H(D) out-of-plane bending vibrations.…”

Section: Secondary A-deuterium Kiesmentioning

confidence: 99%

Determining transition state structure using kinetic isotope effects

Westaway

2007

Labelled Comp Radiopharmac

View full text Add to dashboard Cite

Kinetic isotope effects (KIEs) have been found to be the most powerful tool available to physical organic chemists for determining the mechanism of reactions and for estimating the structure of their transition states. Various types of KIEs including primary-leaving group-, nucleophile-, and a-carbon KIEs and secondary alpha-and beta-deuterium KIEs are introduced. The factors that affect the magnitude of each of these KIEs are covered in some detail. Finally, the use of these KIEs to determine the mechanism of a reaction and to estimate the structure of the transition state for a reaction is discussed.

show abstract

“…6 Experimental studies in bulk non-polar solvents suggest that the hydration state of the anion strongly influences its nucleophilicity. [628][629][630] Much theoretical support for this has also been provided from studies of S N 2 reactions in gas phase clusters [631][632][633] and in bulk liquids. 626,634 Another question revolves around the finding about the strong dependence of solvent polarity on the surface location and orientation.…”

Section: Nucleophilic Substitution Reactions and Phase Transfer Catalmentioning

confidence: 92%

Reactivity and Dynamics at Liquid Interfaces

Benjamin¹

2015

Reviews in Computational Chemistry

View full text Add to dashboard Cite

Solvent and secondary kinetic isotope effects for the microhydrated SN2 reaction of Cl-(H2O)n with CH3Cl

Cited by 140 publications

References 2 publications

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl− attack on CH3Cl

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl− attack on CH3Cl

Determining transition state structure using kinetic isotope effects

Reactivity and Dynamics at Liquid Interfaces

Contact Info

Product

Resources

About