Activation of C-H and B-H bonds through agostic bonding: an ELF/QTAIM insight

Physical Chemistry Chemical Physics : PCCP
Emilie-Laure ZinsMohammad Esmail Alikhani

Abstract

Agostic bonding is of paramount importance in C-H bond activation processes. The reactivity of the σ C-H bond thus activated will depend on the nature of the metallic center, the nature of the ligand involved in the interaction and co-ligands, as well as on geometric parameters. Because of their importance in organometallic chemistry, a qualitative classification of agostic bonding could be very much helpful. Herein we propose descriptors of the agostic character of bonding based on the electron localization function (ELF) and Quantum Theory of Atoms in Molecules (QTAIM) topological analysis. A set of 31 metallic complexes taken, or derived, from the literature was chosen to illustrate our methodology. First, some criteria should prove that an interaction between a metallic center and a σ X-H bond can indeed be described as "agostic" bonding. Then, the contribution of the metallic center in the protonated agostic basin, in the ELF topological description, may be used to evaluate the agostic character of bonding. A σ X-H bond is in agostic interaction with a metal center when the protonated X-H basin is a trisynaptic basin with a metal contribution strictly larger than the numerical uncertainty, i.e. 0.01 e. In addition, it was ...Continue Reading

References

Oct 16, 2001·Inorganic Chemistry·R F Bader, C F Matta
Dec 26, 2001·Chemical Reviews·S Niu, M B Hall
Apr 1, 2004·Angewandte Chemie·Wolfgang Scherer, G Sean McGrady
Jul 30, 2004·Journal of the American Chemical Society·Timo Jacob, William A Goddard
Jan 25, 2006·Chemical Communications : Chem Comm·Tejender S Thakur, Gautam R Desiraju
Apr 13, 2007·Journal of Chemical Information and Modeling·Karen L SchuchardtTheresa L Windus
Apr 20, 2007·Proceedings of the National Academy of Sciences of the United States of America·Maurice BrookhartGerard Parkin
May 25, 2007·Journal of the American Chemical Society·Tülay A AteşinWilliam D Jones
Jun 22, 2007·The Journal of Physical Chemistry. a·Björn O RoosLester Andrews
Jun 28, 2007·Journal of the American Chemical Society·Gilles AlcarazSylviane Sabo-Etienne
Nov 8, 2008·Physical Chemistry Chemical Physics : PCCP·Jeng-Da Chai, Martin Head-Gordon
Apr 29, 2009·Journal of the American Chemical Society·Taryn D ForsterRoland Roesler
Nov 11, 2009·Science·Wesley H BernskoetterMaurice Brookhart
Feb 27, 2010·Angewandte Chemie·Wolfgang SchererPeter W Roesky
Feb 2, 2011·Journal of the American Chemical Society·James A CalladineKhuong Q Vuong
Mar 10, 2011·Angewandte Chemie·Wolfgang SchererDietmar Stalke
Jul 23, 2011·The Journal of Physical Chemistry. a·Franck Fuster, Sławomir J Grabowski
Jun 22, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Matthias LeinAlastair J Nielson
Sep 11, 2013·Chemical Society Reviews·Michel Etienne, Andrew S Weller
Apr 12, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·M G Derry HoladayA Srinivasan

❮ Previous
Next ❯

Citations

Aug 2, 2016·Inorganic Chemistry·Linda S JongbloedJarl Ivar van der Vlugt
Apr 27, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Alain C Tagne KuateF Jäkle
Nov 27, 2016·Journal of Molecular Modeling·Jingwen ZhuMohammad Esmaïl Alikhani
Feb 6, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Pablo CrujeirasAntonio Sousa-Pedrares
Mar 8, 2018·Angewandte Chemie·Qing LuGiovanni Bistoni
Sep 11, 2019·Physical Chemistry Chemical Physics : PCCP·Yann Cornaton, Jean-Pierre Djukic
May 21, 2021·Physical Chemistry Chemical Physics : PCCP·Chen-Hao YehJyh-Chiang Jiang
Feb 19, 2016·Journal of Chemical Theory and Computation·Martin Rahm

❮ 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.

© 2021 Meta ULC. All rights reserved