Halogen Bond Asymmetry in Solution

Journal of the American Chemical Society
Sofia LindbladMáté Erdélyi

Abstract

Halogen bonding is the noncovalent interaction of halogen atoms in which they act as electron acceptors. Whereas three-center hydrogen bond complexes, [D···H···D]+ where D is an electron donor, exist in solution as rapidly equilibrating asymmetric species, the analogous halogen bonds, [D···X···D]+, have been observed so far only to adopt static and symmetric geometries. Herein, we investigate whether halogen bond asymmetry, i.e., a [D-X···D]+ bond geometry, in which one of the D-X bonds is shorter and stronger, could be induced by modulation of electronic or steric factors. We have also attempted to convert a static three-center halogen bond complex into a mixture of rapidly exchanging asymmetric isomers, [D···X-D]+ ⇄ [D-X···D]+, corresponding to the preferred form of the analogous hydrogen bonded complexes. Using 15N NMR, IPE NMR, and DFT, we prove that a static, asymmetric geometry, [D-X···D]+, is obtained upon desymmetrization of the electron density of a complex. We demonstrate computationally that conversion into a dynamic mixture of asymmetric geometries, [D···X-D]+ ⇄ [D-X···D]+, is achievable upon increasing the donor-donor distance. However, due to the high energetic gain upon formation of the three-center-four-electron...Continue Reading

References

Jun 9, 2001·The Journal of Organic Chemistry·M Erdélyi, A Gogoll
Jul 24, 2001·Chemistry : a European Journal·P Metrangolo, G Resnati
Oct 24, 2001·The Journal of Organic Chemistry·Alexei A. Neverov, R. S. Brown
Jan 5, 2002·The Journal of Organic Chemistry·Philippe GrosYves Fort
Sep 8, 2004·Chemistry : a European Journal·José BarluengaJosé M González
May 18, 2005·Accounts of Chemical Research·Pierangelo MetrangoloGiuseppe Resnati
Oct 14, 2010·Accounts of Chemical Research·Charles L Perrin
Nov 16, 2010·Chemical Communications : Chem Comm·Hiromichi FujiokaYasuyuki Kita
Oct 21, 2011·Chemical Communications : Chem Comm·Anna-Carin C CarlssonMáté Erdélyi
Feb 16, 2012·Chemical Society Reviews·Máté Erdélyi
Mar 6, 2012·Journal of the American Chemical Society·Anna-Carin C CarlssonMáté Erdélyi
Nov 14, 2012·Journal of Medicinal Chemistry·Rainer WilckenFrank M Boeckler
Feb 12, 2014·Organic Letters·Silvia Castro-FernándezArmando Navarro-Vázquez
Aug 20, 2014·Accounts of Chemical Research·Arijit MukherjeeGautam R Desiraju
Aug 22, 2014·Nature Chemistry·Mate Erdelyi
Oct 20, 2014·Topics in Current Chemistry·P Shing Ho
Mar 26, 2015·Topics in Current Chemistry·Anna-Carin C CarlssonMáté Erdélyi
Jul 15, 2015·Chemical Reviews·Lydia C GildayPaul D Beer
Sep 9, 2014·Journal of Chemical Theory and Computation·Changwei WangSason Shaik
Jan 6, 2016·Chemical Communications : Chem Comm·Rakesh PuttreddyKari Rissanen
Jan 27, 2016·Chemical Reviews·Gabriella CavalloGiancarlo Terraneo
Jun 7, 2016·Journal of the American Chemical Society·Anna-Carin C CarlssonMáté Erdélyi
Jul 29, 2016·Chemistry : a European Journal·David Bulfield, Stefan M Huber
Nov 26, 2016·Physical Chemistry Chemical Physics : PCCP·Vytor OliveiraDieter Cremer
Jul 27, 2017·Faraday Discussions·Emmanuel AubertMarc Fourmigué
Jul 1, 2015·Chemical Science·Michele BedinMáté Erdélyi

❮ Previous
Next ❯

Citations

May 11, 2019·Angewandte Chemie·Alan VanderkooyMáté Erdélyi
Jun 25, 2020·Chemical Communications : Chem Comm·Jas S WardKari Rissanen
Sep 26, 2020·Physical Chemistry Chemical Physics : PCCP·Justyna Dominikowska
Mar 27, 2020·Chemical Society Reviews·Lotta Turunen, Máté Erdélyi
Mar 25, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Alexei S Ostras'Peter M Tolstoy
Nov 5, 2020·Chemical Communications : Chem Comm·Daniel von der HeidenMáté Erdélyi
Oct 24, 2020·Chemistry : a European Journal·Jenni FroschMatthias Tamm
Nov 11, 2020·Inorganic Chemistry·Ann Christin ReiersølmoenAnne Fiksdahl
Mar 26, 2021·Inorganic Chemistry·Jas S WardKari Rissanen
Mar 18, 2021·Magnetic Resonance in Chemistry : MRC·Stefan KuhnDamien Jeannerat
Apr 21, 2021·Physical Chemistry Chemical Physics : PCCP·Sarah Karbalaei KhaniChristof Hättig
Jun 8, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Jas S WardKari Rissanen
Jun 8, 2021·Chemical Science·Ann Christin ReiersølmoenMáté Erdélyi
Nov 3, 2020·Journal of Chemical Theory and Computation·Daniel SethioMáté Erdélyi
Mar 14, 2020·Journal of the American Chemical Society·Ann Christin ReiersølmoenMáté Erdélyi
Jul 17, 2021·Angewandte Chemie·Shilin YuKari Rissanen
Apr 5, 2019·Journal of the American Chemical Society·Chao WangSason Shaik
Aug 3, 2021·Chemistry : a European Journal·Sofia LindbladMate Erdelyi
Sep 16, 2021·Organic & Biomolecular Chemistry·Daniel von der HeidenMate Erdelyi
Nov 5, 2021·Chemical Communications : Chem Comm·Shilin YuKari Rissanen

❮ Previous
Next ❯

Methods Mentioned

BETA
X-ray
NMR

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.

Related Papers

Journal of the American Chemical Society
Anna-Carin C CarlssonMáté Erdélyi
Journal of the American Chemical Society
Alavi KarimMáté Erdélyi
Topics in Current Chemistry
Anna-Carin C CarlssonMáté Erdélyi
Journal of the American Chemical Society
Anna-Carin C CarlssonMáté Erdélyi
© 2022 Meta ULC. All rights reserved