The ion-pair SN 2 reactions of model systems MnF(n-1) +CH3Cl(M(+) =Li(+), Na(+), K(+), and MgCl(+); n=0, 1) have been quantum chemically explored by using DFT at the OLYP/6-31++G(d,p) level. The purpose of this study is threefold: 1) to elucidate how the counterion M(+) modifies ion-pair SN 2 reactivity relative to the parent reaction F(-) +CH3Cl; 2) to determine how this influences stereochemical competition between the backside and frontside attacks; and 3) to examine the effect of solvation on these ion-pair SN2 pathways. Trends in reactivity are analyzed and explained by using the activation strain model (ASM) of chemical reactivity. The ASM has been extended to treat reactivity in solution. These findings contribute to a more rational design of tailor-made substitution reactions.

We have theoretically studied the non-identity S 2 reactions of M OH +CH Cl (M =Li , Na , K , and MgCl ; n=0, 1) in the gas phase and in THF solution at the OLYP/6-31++G(d,p) level using polarizable continuum model (PCM) implicit solvation. We want to explore and understand the effect of the metal counterion M and solvation on the reaction profile and the stereoselectivity of these processes. To this end, we have explored the potential energy surfaces of the backside (S 2-b) and frontside (S 2-f) pathways. To explain the computed trends, we have carried out analyses with an extended activation strain model (ASM) of chemical reactivity that includes the treatment of solvation effects.

The processing of the input and output files of quantum chemical calculations often necessitates a spreadsheet as a key component of the workflow. Spreadsheet packages with a built-in programming language editor can automate the steps involved and thus provide a direct link between processing files and the spreadsheet. This helps to reduce user-interventions as well as the need to switch between different programs to carry out each step. The ExcelAutomat tool is the implementation of this method in Microsoft Excel (MS Excel) using the default Visual Basic for Application (VBA) programming language. The code in ExcelAutomat was adapted to work with the platform-independent open-source LibreOffice Calc, which also supports VBA. ExcelAutomat provides an interface through the spreadsheet to automate repetitive tasks such as merging input files, splitting, parsing and compiling data from output files, and generation of unique filenames. Selected extracted parameters can be retrieved as variables which can be included in custom codes for a tailored approach. ExcelAutomat works with Gaussian files and is adapted for use with other computational packages including the non-commercial GAMESS. ExcelAutomat is available as a downloadable MS Excel workbook or as a LibreOffice workbook.

We have computationally studied the bimolecular nucleophilic substitution (SN2) reactions of MnNH2(n−1) + CH3Cl (M+ = Li+, Na+, K+, and MgCl+; n = 0, 1) in the gas phase and in tetrahydrofuran solution at OLYP/6‐31++G(d,p) using polarizable continuum model implicit solvation. We wish to explore and understand the effect of the metal counterion M+ and of solvation on the reaction profile and the stereochemical preference, that is, backside (SN2‐b) versus frontside attack (SN2‐f). The results were compared to the corresponding ion‐pair SN2 reactions involving F− and OH− nucleophiles. Our analyses with an extended activation strain model of chemical reactivity uncover and explain various trends in SN2 reactivity along the nucleophiles F−, OH−, and , including solvent and counterion effects. © 2019 Wiley Periodicals, Inc.

The distortion/interaction-activation strain model (D/I-ASM), a fragment analysis method, is applied to study the structure-reactivity relationship in reactions. The application of D/I-ASM involves the generation of input files for points along a reaction profile, submission of input files to a quantum software package, processing of parameters from the resulting output files and generation of graphical plots. The ExcelAutomat tool (Laloo et al., J. Comput. Aided Mol. Des. 2017, 31, 667) provides a framework and library in Visual Basic for Application programming language to process such files. New routines were written in ExcelAutomat 1.3 to facilitate processing of files for D/I-ASM. The worksheet "ASM" was included where initial parameters needed can be defined. The routines for D/I-ASM were tested successfully on bimolecular nucleophilic substitution, cycloaddition, and barrierless reactions. The automation of fragment analysis by ExcelAutomat 1.3 is compatible with Microsoft Excel and LibreOffice Calc. The extensible tool processes files from Gaussian and GAMESS-US packages.