Work

Nuclear Quantum Effects on the Nature of Hydroboration Selectivity: Experimental Effects of First-Collision Tunneling

Year: 2024

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide The understanding of selectivity in reactions exhibiting nonstatistical dynamics is impeded by the limitations of trajectory studies with regard to nuclear quantum effects, especially tunneling. We described here the use of ring-polymer molecular dynamics (RPMD) to account for an unusual regiochemical isotope effect on the regioselectivity of hydroborations of alkenes with BH 3 /BD 3 . RPMD is able to account for the experimental observation, while statistical approaches and classical trajectories fail. The combination of experiment and RPMD trajectories suggests that tunneling in the initial collision of reactants is the major source of the nonstatistical selectivity.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.4c09306

Authors: Christoph E. Bracher, Connor J. Allen, Daniel A. Singleton

Institution: Texas A&M University

Language: English

Topic: Organoboron and organosilicon chemistry

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: National Science Foundation, Welch Foundation, Division of Chemistry