3 years ago

Mapping the Trajectory of Nucleophilic Substitution at Silicon Using a peri-Substituted Acenaphthyl Scaffold

Mapping the Trajectory of Nucleophilic Substitution at Silicon Using a peri-Substituted Acenaphthyl Scaffold
Malte Fugel, Simon Grabowsky, Marian Olaru, Enno Lork, Ciprian I. Raţ, Emanuel Hupf, Jens Beckmann, Christian B. Hübschle, Stefan Mebs
The second-order nucleophilic substitution (SN2) reaction at a silicon atom is scrutinized by means of snapshots along a pseudoreaction coordinate. Phosphine and fluoride represent both attacking and leaving groups in the modeled SN2 reaction. In the experimentally obtained 5-diphenylphosphinoacenaphth-6-yl-dimethylfluorosilane, 1, the phosphine and fluorosilane moieties are forced into immediate proximity through an acenaphthyl scaffold, that is, they exhibit peri interactions that serve as the model of the reactant ion–molecule complex and starting point for a theoretical potential-energy surface (PES) scan. Upon dissociation of fluoride, the experimentally obtained silylphosphonium cation 2 serves as a model of the product and end point of the PES scan. The pseudoreaction pathway is studied using geometric, energetic, spectroscopic, molecular-orbital, and topological real-space bonding indicators. It becomes evident that it is crucial to combine such methods to understand the pseudoreaction because they reveal different aspects based on different sensitivity to dispersive, electrostatic, and polar-covalent contributions to bonding, as shown by the reduced density gradient analysis. For example, atoms-in-molecules theory describes a late topological catastrophe, whereas the electron localizability indicator describes an early concerted reaction and natural resonance theory describes a more gradual change of properties. This case study encourages the use of a well-balanced toolbox equipped with complementary methods to emphasize different aspects of bonding. Finding the way: A toolbox of bonding descriptors leads to a detailed picture of the trajectory of a second-order nucleophilic substitution (SN2) reaction at silicon. Experimental results are compared with results from different computational methods for a detailed understanding of the progress of the reaction.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201700992

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