Electron flow in reaction mechanisms--revealed from first principles

Angewandte Chemie
Gerald Knizia, Johannes E M N Klein

Abstract

The "curly arrow" of Robinson and Ingold is the primary tool for describing and rationalizing reaction mechanisms. Despite this approach's ubiquity and stellar success, its physical basis has never been clarified and a direct connection to quantum chemistry has never been found. Here we report that the bond rearrangements expressed by curly arrows can be directly observed in ab initio computations, as transformations of intrinsic bond orbitals (IBOs) along the reaction coordinate. Our results clarify that curly arrows are rooted in physical reality-a notion which has been challenged before-and show how quantum chemistry can directly establish reaction mechanisms in intuitive terms and unprecedented detail.

References

Feb 6, 2007·The Journal of Physical Chemistry. a·Xiaoyan LiShijun Zheng
Apr 10, 2008·The Journal of Chemical Physics·Daniel SheppardGraeme Henkelman
Aug 30, 2008·Physical Chemistry Chemical Physics : PCCP·Dmitry Yu Zubarev, Alexander I Boldyrev
Jul 10, 2009·Physical Chemistry Chemical Physics : PCCP·Giuliano BandoliGloria Tabacchi
Jun 10, 2010·Accounts of Chemical Research·Sason ShaikYong Wang
Jan 26, 2011·The Journal of Physical Chemistry. B·Dirk AndraeBeate Paulus
Mar 2, 2013·Angewandte Chemie·Tobias HavenMeike Niggemann
Feb 1, 2014·Angewandte Chemie·Johannes E M N KleinBernd Plietker
May 13, 2014·Chemistry : a European Journal·Johannes E M N KleinBernd Plietker
Feb 11, 2014·Journal of Chemical Theory and Computation·Susi Lehtola, Hannes Jónsson
Nov 12, 2013·Journal of Chemical Theory and Computation·Gerald Knizia
Aug 12, 2014·Journal of Chemical Theory and Computation·Tomasz Janowski

❮ Previous
Next ❯

Citations

Dec 24, 2015·Journal of the American Chemical Society·Debanjan DharWilliam B Tolman
Jan 2, 2016·The Journal of Physical Chemistry Letters·Nico Holmberg, Kari Laasonen
Mar 31, 2016·Journal of Chemical Information and Modeling·Zhaomin LiuNicolas Moitessier
Feb 10, 2017·The Journal of Organic Chemistry·Michelle BezansonNicolas Moitessier
May 31, 2017·The Journal of Organic Chemistry·Joshua P PetersonArthur H Winter
Sep 16, 2016·Angewandte Chemie·Dominik MunzGuy Bertrand
Dec 30, 2015·Chemistry : a European Journal·A Stephen K Hashmi
Oct 6, 2015·Chemical Communications : Chem Comm·Marta Ayerbe GarciaRené Peters
Jul 18, 2015·Physical Chemistry Chemical Physics : PCCP·Adam J ProudJason K Pearson
Jun 9, 2017·Chemistry : a European Journal·Laura Nunes Dos Santos CompridoA Stephen K Hashmi
Jul 22, 2017·Journal of Chemical Theory and Computation·Elvira R SayfutyarovaGerald Knizia
Nov 15, 2017·Angewandte Chemie·Holger BraunschweigJonas H Muessig
Mar 29, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Rong ShangYohsuke Yamamoto
Sep 19, 2017·Chemistry : a European Journal·Johannes E M N KleinA Stephen K Hashmi
Oct 28, 2017·Physical Chemistry Chemical Physics : PCCP·Juan AndrésBernard Silvi
Sep 8, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Svea HinrichsenFelix Tuczek
Aug 16, 2017·Physical Chemistry Chemical Physics : PCCP·Stefan SchrammPanče Naumov
Jan 18, 2018·Chemistry : a European Journal·Johannes E M N KleinGerald Knizia
Jul 19, 2018·Angewandte Chemie·Johannes E M N Klein, Gerald Knizia
Sep 11, 2018·Physical Chemistry Chemical Physics : PCCP·Weiguo SunAndreas Hermann
Sep 4, 2018·Angewandte Chemie·Moritz MalischewskiKarsten Meyer
May 3, 2018·Angewandte Chemie·Sergei I IvlevFlorian Kraus
Apr 11, 2019·Chemistry : a European Journal·Youngsuk KimDouglas W Stephan
May 1, 2019·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Diego SorbelliJohannes E M N Klein
Jun 28, 2019·Chemistry : a European Journal·Pablo RíosSalvador Conejero
Jun 18, 2019·Angewandte Chemie·Jelte S SteenJohannes E M N Klein
Apr 30, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Magnus R BuchnerNils Spang
May 1, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Xu ZhangZhongshu Li
May 21, 2020·Organic & Biomolecular Chemistry·Rodrigo Ormazábal-ToledoSebastián Gallardo-Fuentes
Jul 2, 2020·Angewandte Chemie·Benjamin ScheibeFlorian Kraus
May 8, 2015·Angewandte Chemie·Laura Nunes Dos Santos CompridoA Stephen K Hashmi
Apr 12, 2016·Angewandte Chemie·Sara SzymkućBartosz A Grzybowski
Apr 21, 2018·Chemical Science·Dominik Munz
Oct 18, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Giuseppe SciortinoPietro Vidossich
Jan 16, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Martí GimferrerPedro Salvador
Oct 7, 2015·Chemistry : a European Journal·Luis CasarrubiosMiguel A Sierra

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.