Directing isomerization reactions of cumulenes with electric fields

• DOI: 10.1038/s41467-019-12487-w
• Publication Date: 2019-10-02T10:05:38Z
• Authors: Yaping Zang; Qi Zou; Tianren Fu; Fay Ng; Brandon Fowler; Jingjing Yang; Hexing Li; Michael L. Steige...; Colin Nuckolls; Latha Venkataraman
• Keywords: Transition state; Transition state theory

Abstract Electric fields have been proposed as having a distinct ability to catalyze chemical reactions through the stabilization of polar or ionic intermediate transition states. Although field-assisted catalysis is being researched, in solution using electric remains elusive and understanding mechanisms such sparse. Here we show that an field can cis-to-trans isomerization [3]cumulene derivatives solution, scanning tunneling microscope. We further external alter thermodynamics inhibiting trans-to-cis reverse reaction, endowing selectivity toward trans isomer. Using density functional theory-based calculations, find applied promotes zwitterionic resonance form, which ensures lower energy state for reaction. The also stabilizes relative cis, dictating cis/trans thermodynamics, driving equilibrium product exclusively trans.