Novel pnicogen bonding interactions with silylene as an electron donor: covalency, unusual substituent effects and new mechanisms

Physical Chemistry Chemical Physics : PCCP
Hongying Zhuo, Qingzhong Li

Abstract

An analogue of carbene, singlet silylene (H3P=N)2Si, was paired with the mono-substituted phosphines XH2Y (X = P, As, and Sb; Y = F, Cl, Br, and I) to form unconventional pnicogen-bonded complexes. All structures have Cs symmetry except the Sb complex, showing a deviation from this symmetry due to the coexistence of H···H interactions. The P and As complexes have different geometries from conventional pnicogen-bonded ones because the Y-X···Si line shows a large deviation from the molecular plane composed of two N atoms and one Si atom of (H3P=N)2Si. This deviation can be attributed to a new formation mechanism of the pnicogen bond due to the combined result of the LPSi→ BD*X-Y and LPX→ LP*Si orbital interactions. Generally, the pnicogen bond becomes stronger in the order of F < Cl < Br < I and weaker in the order of P > As > Sb, exhibiting an unexpected substitution effect and dependence on the nature of the pnicogen atom. These orders are inconsistent with the MEP on the X atom but can be better explained by the above orbital interactions. The Si···X interaction displays a character of covalent or partially covalent interaction, evidenced by the high interaction energy of -59.9 to -105.4 kJ mol(-1) as well as the negative ener...Continue Reading

References

Mar 5, 2008·Journal of Molecular Modeling·Peter PolitzerMonica C Concha
Aug 6, 2008·The Journal of Physical Chemistry. a·Janet E Del BeneJosé Elguero
Dec 3, 2009·The Journal of Physical Chemistry. a·Qingzhong LiJiazhong Sun
Jun 24, 2010·Physical Chemistry Chemical Physics : PCCP·Peter PolitzerTimothy Clark
Jan 19, 2011·The Journal of Chemical Physics·Mohammad SolimannejadSteve Scheiner
Feb 17, 2011·Chemical Reviews·Sławomir Janusz Grabowski
Mar 10, 2011·The Journal of Chemical Physics·Steve Scheiner
Apr 20, 2011·Chemistry : a European Journal·Stefan ZahnBarbara Kirchner
Jul 7, 2011·The Journal of Physical Chemistry. a·Steve Scheiner
Jul 9, 2011·The Journal of Physical Chemistry. a·Ángel Sánchez-GonzálezJuan Andrés
Sep 10, 2011·The Journal of Physical Chemistry. a·Steve Scheiner, Upendra Adhikari
Nov 18, 2011·The Journal of Chemical Physics·Upendra Adhikari, Steve Scheiner
Dec 14, 2011·Journal of Computational Chemistry·Tian Lu, Feiwu Chen
Feb 23, 2012·The Journal of Physical Chemistry. a·Qing-Zhong LiJian-Bo Cheng
Sep 20, 2012·Physical Chemistry Chemical Physics : PCCP·Antonio BauzáAntonio Frontera
Nov 9, 2012·Accounts of Chemical Research·Steve Scheiner
Dec 22, 2012·The Journal of Physical Chemistry. a·Ibon AlkortaJanet E Del Bene
Mar 2, 2013·Physical Chemistry Chemical Physics : PCCP·Peter PolitzerTimothy Clark
Mar 5, 2013·Journal of Molecular Modeling·Mehdi D Esrafili, Nafiseh Mohammadirad
Mar 16, 2013·The Journal of Physical Chemistry. a·Abul Kalam BiswasBishwajit Ganguly
Jun 5, 2013·The Journal of Physical Chemistry. a·Ibon AlkortaJanet E Del Bene
Jul 24, 2013·Physical Chemistry Chemical Physics : PCCP·Goar Sánchez-SanzJosé Elguero
Sep 10, 2013·Journal of Molecular Modeling·Mehdi D EsrafiliParvin Esmailpour
Sep 21, 2013·The Journal of Physical Chemistry. a·Ibon AlkortaJanet E Del Bene
Jan 18, 2014·The Journal of Physical Chemistry. a·Ibon AlkortaMohammad Solimannejad
Mar 5, 2014·The Journal of Physical Chemistry. a·Liangyu Guan, Yirong Mo
Apr 26, 2014·The Journal of Physical Chemistry. a·Janet E Del BeneJosé Elguero
Jun 26, 2014·Physical Chemistry Chemical Physics : PCCP·Goar Sánchez-SanzJosé Elguero

❮ Previous
Next ❯

Citations

Jan 12, 2016·Physical Chemistry Chemical Physics : PCCP·Vincent de Paul N Nziko, Steve Scheiner
May 15, 2015·The Journal of Physical Chemistry. a·Vincent de Paul N Nziko, Steve Scheiner
Mar 28, 2017·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Janet E Del BeneJosé Elguero
Jul 11, 2021·Journal of Molecular Modeling·Chunhong ZhaoXueying Zhang

❮ 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.