Competition between Orbitals and Stress in Mechanochemistry

被引：42

作者：

Kochhar, Gurpaul S. ^{[1
]}

Bailey, Adrian ^{[1
]}

Mosey, Nicholas J. ^{[1
]}

机构：

[1] Queens Univ, Dept Chem, Kingston, ON K7L 3N6, Canada

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2010年 / 49卷 / 41期

基金：

加拿大自然科学与工程研究理事会;

关键词：

computational chemistry; mechanochemistry; pericyclic reactions; Woodward-Hoffmann rules; CIS-BUTADIENE; BONDS; CYCLOBUTENE; PATHWAYS; DYNAMICS; FORCE;

D O I：

10.1002/anie.201003978

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Stress test: Quantum chemical methods were used to study how subjecting molecules to mechanical stresses (see picture; Fext is an external force) can overcome the Woodward-Hoffmann (WH) rules. The results show that applied stresses do not alter the electronic structure (as is the case for irradiation) but rather render the WH rules secondary to mechanochemical factors that favor progression to the products. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：7452 / 7455

页数：4

共 18 条

[1]

[Anonymous], ANGEW CHEM

[2] Mechanochemistry: The mechanical activation of covalent bonds [J].

Beyer, MK ;

Clausen-Schaumann, H .

CHEMICAL REVIEWS, 2005, 105 (08) :2921-2948

[3] CONROTATORY AND DISROTATORY STATIONARY-POINTS FOR THE ELECTROCYCLIC ISOMERIZATION OF CYCLOBUTENE TO CIS-BUTADIENE [J].

BREULET, J ;

SCHAEFER, HF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (05) :1221-1226

[4] Mechanical processes in biochemistry [J].

Bustamante, C ;

Chemla, YR ;

Forde, NR ;

Izhaky, D .

ANNUAL REVIEW OF BIOCHEMISTRY, 2004, 73 :705-748

[5] Dynamic strength of molecular adhesion bonds [J].

Evans, E ;

Ritchie, K .

BIOPHYSICAL JOURNAL, 1997, 72 (04) :1541-1555

[6]

Gordon MS, 2005, THEORY AND APPLICATIONS OF COMPUTATIONAL CHEMISTRY: THE FIRST FORTY YEARS, P1167, DOI 10.1016/B978-044451719-7/50084-6

[7] Biasing reaction pathways with mechanical force [J].

Hickenboth, Charles R. ;

Moore, Jeffrey S. ;

White, Scott R. ;

Sottos, Nancy R. ;

Baudry, Jerome ;

Wilson, Scott R. .

NATURE, 2007, 446 (7134) :423-427

[8] CANONICAL DYNAMICS - EQUILIBRIUM PHASE-SPACE DISTRIBUTIONS [J].

HOOVER, WG .

PHYSICAL REVIEW A, 1985, 31 (03) :1695-1697

[9] Mechanochemistry and thermochemistry are different: Stress-induced strengthening of chemical bonds [J].

Konopka, Martin ;

Turansky, Robert ;

Reichert, Joachim ;

Fuchs, Harald ;

Marx, Dominik ;

Stich, Ivan .

PHYSICAL REVIEW LETTERS, 2008, 100 (11)

[10] First Principles Dynamics and Minimum Energy Pathways for Mechanochemical Ring Opening of Cyclobutene [J].

Ong, Mitchell T. ;

Leiding, Jeff ;

Tao, Hongli ;

Virshup, Aaron M. ;

Martinez, Todd J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (18) :6377-+

← 1 2 →