Nucleophilic substitution at silicon (SN2@Si) via a central reaction barrier

It is textbook knowledge that nucleophilic substitution at carbon (S(N)2@C) proceeds via a central reaction barrier which disappears in the corresponding nucleophilic substitution reaction at silicon (S(N)2@ Si). Here, we address the question why the central barrier disappears from S(N)2@ C to S(N)2@ Si despite the fact that these processes are isostructural and isoelectronic. To this end, we have explored and analyzed the potential energy surfaces (PES) of various Cl- + CR3Cl (R = H, CH3) and Cl- + SiR3Cl model reactions (R = H, CH3, C2H5, and OCH3). Our results show that the nature of the S(N)2 reaction barrier is in essence steric, but that it can be modulated by electronic factors. Thus, simply by increasing the steric demand of the substituents R around the silicon atom, the S(N)2@ Si mechanism changes from its regular single-well PES (with a stable intermediate transition complex, TC), via a triple- well PES (with a pre- and a post-TS before and after the central TC), to a double-well PES (with a TS; R = OCH3), which is normally encountered for S(N)2@C reactions.