Transition between [R]- and [S]-stereoisomers without bond breaking. Issue 26 (26th June 2020)

• Record Type: Journal Article
• Authors: Raghunathan, Shampa; Yadav, Komal; Rojisha, V. C.; Jaganade, Tanashree; Prathyusha, V.; Bikkina, Swetha; Lourderaj, Upakarasamy; Priyakumar, U. Deva
• Is Part Of: Physical chemistry chemical physics. Volume 22:Issue 26(2020)
• Page Start: 14983
• Page End: 14991
• Publication Date: 2020-06-26
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d0cp02918a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : First examples of racemization of tetrahedral tetracoordinated centers via a planar transition state or an intermediate structure. Abstract : The fifty-year old proposal of a nondissociative racemization reaction of a tetracoordinated tetrahedral center from one enantiomer to another via a planar transition state by Hoffmann and coworkers has been explored by many research groups over the past five decades. A number of stable molecules with planar tetracoordinated and higher-coordinated centers have been designed and experimentally realized; however, there has not been a single example of a molecular system that can possibly undergo such racemization. Here we show examples of molecular species that undergo inversion of stereochemistry around tetrahedral centers (Si, Al − and P + ) either via a planar transition state or an intermediate state using quantum mechanical, ab initio quasi-classical dynamics calculations, and Born–Oppenheimer molecular dynamics (BOMD) simulations. This work is expected to provide potential leads for future studies on this fundamental phenomenon in chemistry.