Hydrogen-abstraction reactivity patterns from A to Y: the valence bond way

Angewandte Chemie
Wenzhen LaiSason Shaik

Abstract

"Give us insight, not numbers" was Coulson's admonition to theoretical chemists. This Review shows that the valence bond (VB)-model provides insights and some good numbers for one of the fundamental reactions in nature, the hydrogen-atom transfer (HAT). The VB model is applied to over 50 reactions from the simplest H + H(2) process, to P450 hydroxylations and H-transfers among closed-shell molecules; for each system the barriers are estimated from raw data. The model creates a bridge to the Marcus equation and shows that H-atom abstraction by a closed-shell molecule requires a higher barrier owing to the additional promotion energy needed to prepare the abstractor for H-abstraction. Under certain conditions, a closed-shell abstractor can bypass this penalty through a proton-coupled electron transfer (PCET) mechanism. The VB model links the HAT and PCET mechanisms conceptually and shows the consequences that this linking has for H-abstraction reactivity.

References

Jul 1, 1996·Protein Engineering·M D Paulsen, R L Ornstein
Feb 6, 1999·Annual Review of Physical Chemistry·R I Cukier, D G Nocera
Dec 14, 1999·Angewandte Chemie·T WistubaP Kircher
Aug 5, 2000·Chemistry : a European Journal·C Limberg
Apr 20, 2001·Accounts of Chemical Research·S Hammes-Schiffer
May 7, 1997·Inorganic Chemistry·Kimberly A. GardnerJames M. Mayer
Oct 25, 2001·The Journal of Organic Chemistry·K. N. Houk, Thomas Strassner
Feb 19, 2002·Chemical Reviews·JoAnne Stubbe, Wilfred A. van Der Donk
Jun 19, 2002·Accounts of Chemical Research·Donald G TruhlarJordi Villà
Aug 28, 2002·Natural Product Reports·Paul R Ortiz de Montellano, James J De Voss
Nov 5, 2002·Current Opinion in Chemical Biology·Sason ShaikDetlef Schröder
Nov 5, 2002·Current Opinion in Chemical Biology·Behnaz Behrouzian, Peter H Buist
Jun 12, 2003·Chemical Reviews·Christophe Colas, Paul R Ortiz de Montellano
Jun 12, 2003·Chemical Reviews·Mu-Hyun BaikStephen J Lippard
Aug 20, 2003·Journal of Computational Chemistry·Tadafumi UchimaruAkira Sekiya
Sep 17, 2003·Accounts of Chemical Research·Dirk V Deubel, Gernot Frenking
Jan 15, 2004·Journal of the American Chemical Society·József KaizerLawrence Que
Mar 26, 2004·Natural Product Reports·Peter H Buist
May 1, 2004·Annual Review of Physical Chemistry·James M Mayer
Jul 21, 2004·Accounts of Chemical Research·Brian G FoxCorina E Rogge
Sep 9, 2004·Chemical Reviews·Bernard MeunierSason Shaik
Oct 14, 2004·Journal of the American Chemical Society·Peifeng SuSason Shaik
Apr 5, 2005·Critical Reviews in Biochemistry and Molecular Biology·Michael J McLeish, George L Kenyon
Jun 9, 2005·Chemical Reviews·Sason ShaikWalter Thiel
Dec 27, 2005·The Journal of Physical Chemistry. B·Avital Shurki, Hadar A Crown
Jun 29, 2006·Journal of the American Chemical Society·Hajime HiraoSason Shaik
Jul 13, 2006·The Journal of Physical Chemistry. a·Jason M GonzalesHenry F Schaefer
Jul 22, 2006·Angewandte Chemie·Detlef Schröder, Jana Roithová
Nov 30, 2006·Journal of the American Chemical Society·Alex M KhenkinRonny Neumann
May 1, 2007·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·G Theodoor de Jong, F Matthias Bickelhaupt
May 10, 2007·The Journal of Physical Chemistry. a·Jingjing ZhengDonald G Truhlar
Jun 5, 2007·Accounts of Chemical Research·Carsten KrebsJ Martin Bollinger
Aug 7, 2007·The Journal of Organic Chemistry·Yingsheng WangIan R Gould
Aug 10, 2007·Journal of the American Chemical Society·Daniel H Ess, K N Houk

❮ Previous
Next ❯

Citations

Jul 26, 2012·Journal of the American Chemical Society·Xiaoshi WangJohn T Groves
Sep 16, 2015·Organic Letters·Alexander WagnerArmin R Ofial
Apr 14, 2016·Accounts of Chemical Research·Manoj KumarJoseph S Francisco
Jun 13, 2015·The Journal of Physical Chemistry. a·Xabier LopezJesus M Ugalde
Aug 16, 2016·Journal of the American Chemical Society·Jilai LiHelmut Schwarz
Oct 28, 2015·Journal of the American Chemical Society·Lei WangLiang Deng
Mar 11, 2017·Chemical Reviews·Xiao-Song XueJin-Pei Cheng
Feb 22, 2017·Chemistry : a European Journal·Hendrik HerrmannHans-Jörg Himmel
May 10, 2016·Angewandte Chemie·Shaodong ZhouHelmut Schwarz
Dec 15, 2016·Chemical Reviews·Zhixun LuoShiv N Khanna
Dec 13, 2016·Chemistry : a European Journal·Xiaoyan SunHelmut Schwarz
Aug 19, 2015·Chemical Communications : Chem Comm·Sujoy RanaDebabrata Maiti
May 3, 2018·Physical Chemistry Chemical Physics : PCCP·Anagh MukherjeeKumar Vanka
May 28, 2016·Physical Chemistry Chemical Physics : PCCP·Amol Baliram Patil, Bhalchandra Mahadeo Bhanage
Oct 27, 2016·Physical Chemistry Chemical Physics : PCCP·Athanasios AthanasiadisMarina K Kuimova
Aug 12, 2016·Angewandte Chemie·Shaodong ZhouHelmut Schwarz
Jan 13, 2015·Chemistry : a European Journal·Konstantin L IvanovMikhail Ya Melnikov
Apr 28, 2017·Angewandte Chemie·F Matthias Bickelhaupt, Kendall N Houk
Jan 31, 2013·Angewandte Chemie·Sason ShaikRoald Hoffmann
Aug 10, 2018·Chemistry : a European Journal·Shaodong ZhouHelmut Schwarz

❮ 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.