Ab Initio Molecular Dynamics with Explicit Solvent Reveals a Two‐Step Pathway in the Frustrated Lewis Pair Reaction

Pu, Maoping; Privalov, Timofei

doi:10.1002/chem.201502926

Cited by 23 publications

(25 citation statements)

References 59 publications

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“…Our previous studies concerning A•••B complexes with B being CO2 are reported in references [36][37][38][39][40][41]. Simulation of phosphorous/boron frustrated lewis pair complexes (FLP) with CO2 in explicit solvent proposed a two-step mechanism [42]. The effect of the solvent has been considered on the carbene + CO2 reaction [43,44] and in the anion + CO2 one [45].…”

Section: Resultsmentioning

confidence: 99%

Solvent and Substituent Effects on the Phosphine + CO2 Reaction

et al. 2018

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A theoretical study of the substituent and solvent effects on the reaction of phosphines with CO2 has been carried out by means of Møller-Plesset (MP2) computational level calculations and continuum polarizable method (PCM) solvent models. Three stationary points along the reaction coordinate have been characterized, a pre-transition state (TS) assembly in which a pnicogen bond or tetrel bond is established between the phosphine and the CO2 molecule, followed by a transition state, and leading finally to the adduct in which the P–C bond has been formed. The solvent effects on the stability and geometry of the stationary points are different. Thus, the pnicogen bonded complexes are destabilized as the dielectric constant of the solvent increases while the opposite happens within the adducts with the P–C bond and the TSs trend. A combination of the substituents and solvents can be used to control the most stable minimum.

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Section: Resultsmentioning

confidence: 99%

Solvent and Substituent Effects on the Phosphine + CO2 Reaction

et al. 2018

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“…It is important to note the still approximate nature of such simulations: the approximations used may result in artifacts, such as over‐structured water . At the moment, a few small molecules surrounded by less that 100 water molecules can be simulated by these methods on ∼ 10 ps time‐scale, enough to investigate a chemical reaction pathway . These time‐scales are not comparable to what is now possible with classical water models: 10 μs is becoming routine, and the cutting edge simulations begin to reach into milliseconds.…”

Section: Explicit Water Modelsmentioning

confidence: 99%

Water models for biomolecular simulations

Onufriev

Izadi²

2017

WIREs Comput Mol Sci

169

225

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Modern simulation and modeling approaches to investigation of biomolecular structure and function rely heavily on a variety of methods—water models—to approximate the influence of solvent. We give a brief overview of several distinct classes of available water models, with the emphasis on the conceptual basis at each level of approximation. The main focus is on classes of models most widely used in atomistic simulations, including popular implicit and explicit solvent models. Among the latter, nonpolarizable N‐point models are covered in most detail, including some recent methodological advances and nuances. Notes on practical availability and usage in biomolecular simulations are included. Atomistic simulations that were hardly possible only a short while ago have revealed significant problems that can be traced to deficiencies of most commonly used N‐point water models. Recently developed models of this class approximate experimental properties of liquid water much closer than before, and show promise in practical biomolecular simulations. Obstacles to wider adoption of these more accurate water models, both technical and conceptual, are discussed. It is argued that verifying robustness of simulation results to the choice of water model can be of immediate benefit even in the absence of a clear replacement for older models; a specific strategy is proposed. The review is concluded with a discussion on how force‐field development efforts can benefit from better solvent models, and vice versa. WIREs Comput Mol Sci 2018, 8:e1347. doi: 10.1002/wcms.1347 This article is categorized under: Structure and Mechanism > Computational Biochemistry and Biophysics Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods

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“…fixed charge force fields, polarisable force fields and hybrid quantum mechanics/molecular mechanics (QM/MM) potentials. [15][16][17] There has been some success in the application of explicit solvent models to predict organic and inorganic reaction mechanisms, [18][19][20] electrochemistry, [21][22][23][24][25][26][27] and pKa values. [28][29][30][31] However, given the size of these systems and the need for extensive configurational sampling, explicit solvent simulations are generally carried out using classical MM force fields or hybrid QM/MM potentials.…”

Section: Introductionmentioning

confidence: 99%