Flyby reaction trajectories: Chemical dynamics under extrinsic force

doi:10.1126/science.abi7609

GSTDTAP > 气候变化

DOI	10.1126/science.abi7609
	Flyby reaction trajectories: Chemical dynamics under extrinsic force
	Yun Liu; Soren Holm; Jan Meisner; Yuan Jia; Qiong Wu; Toby J. Woods; Todd J. Martinez; Jeffrey S. Moore
	2021-07-09
发表期刊	Science
出版年	2021
英文摘要	Chemical reactions typically proceed by distributing energy statistically among all accessible molecular vibrations. Liu et al. report that external shear forces can sometimes pry open strained carbon rings without dissipating energy into adjacent bond rotations. Through careful design and synthesis of polymer-embedded cyclobutyl rings, the authors showed that certain relative substituent geometries are preserved when sonication induces ring opening. Accompanying simulations support the instigation of “flyby” trajectories that channel energy narrowly to cleave the cyclic sigma bonds and then rapidly form acyclic pi bonds. Science , abi7609, this issue p. [208][1] Dynamic effects are an important determinant of chemical reactivity and selectivity, but the deliberate manipulation of atomic motions during a chemical transformation is not straightforward. Here, we demonstrate that extrinsic force exerted upon cyclobutanes by stretching pendant polymer chains influences product selectivity through force-imparted nonstatistical dynamic effects on the stepwise ring-opening reaction. The high product stereoselectivity is quantified by carbon-13 labeling and shown to depend on external force, reactant stereochemistry, and intermediate stability. Computational modeling and simulations show that, besides altering energy barriers, the mechanical force activates reactive intramolecular motions nonstatistically, setting up “flyby trajectories” that advance directly to product without isomerization excursions. A mechanistic model incorporating nonstatistical dynamic effects accounts for isomer-dependent mechanochemical stereoselectivity. [1]: /lookup/doi/10.1126/science.abi7609
领域	气候变化 ; 资源环境
URL	查看原文
引用统计
文献类型	期刊论文
条目标识符	http://119.78.100.173/C666/handle/2XK7JSWQ/334271
专题	气候变化资源环境科学
推荐引用方式 GB/T 7714	Yun Liu,Soren Holm,Jan Meisner,et al. Flyby reaction trajectories: Chemical dynamics under extrinsic force[J]. Science,2021.
APA	Yun Liu.,Soren Holm.,Jan Meisner.,Yuan Jia.,Qiong Wu.,...&Jeffrey S. Moore.(2021).Flyby reaction trajectories: Chemical dynamics under extrinsic force.Science.
MLA	Yun Liu,et al."Flyby reaction trajectories: Chemical dynamics under extrinsic force".Science (2021).