High-Level Systematic Ab Initio Comparison of Carbon- and Silicon-Centered SN2 Reactions

We characterize the stationary points along the Walden inversion, front-side attack, and double-inversion pathways of the X– + CH3Y and X– + SiH3Y [X, Y = F, Cl, Br, I] SN2 reactions using chemically accurate CCSD­(T)-F12b/aug-cc-pVnZ [n = D, T, Q] levels of theory. At the carbon center, Walden inversion dominates and proceeds via prereaction (X–···H3CY) and postreaction (XCH3···Y–) ion-dipole wells separated by a usually submerged transition state (X–H3C–Y)−, front-side attack occurs over high barriers, double inversion is the lowest-energy retention pathway for X = F, and hydrogen- (F–···HCH2Y) and halogen-bonded (X–···YCH3) complexes exist in the entrance channel. At the silicon center, Walden inversion proceeds through a single minimum (X–SiH3–Y)−, the front-side attack is competitive via a usually submerged transition state separating pre- and postreaction minima having X–Si–Y angles close to 90°, double inversion occurs over positive, often high barriers, and hydrogen- and halogen-bonded complexes are not found. In addition to the SN2 channels (Y– + CH3X/SiH3X), we report reaction enthalpies for proton abstraction (HX + CH2Y–/SiH2Y–), hydride substitution (H– + CH2XY/SiH2XY), XH···Y– complex formation (XH···Y– + 1CH2/1SiH2), and halogen abstraction (XY + CH3–/SiH3– and XY– + CH3/SiH3).