NDLI: Oxygenation of the phenylhalocarbenes. Are they spin-allowed or spin-forbidden reactions?

Content Provider	Springer Nature Link
Author	Lamsabhi, Al Mokhtar Corral, Inés Pérez, Patricia Tapia, Orlando Yáñez, Manuel
Copyright Year	2011
Abstract	Oxygenation mechanisms of phenylhalocarbenes in vacuum are investigated through the use of density functional theory and CASSCF-PT2 approaches. Reactions with both substituted and unsubstituted phenylhalocarbenes are strongly exothermic. The reactions with nitrosubstituted halocarbenes are predicted to be spin allowed due to the practical degeneracy of the singlet and triplet carbene states. Conversely, for the unsubstituted compounds, the equilibrium between the triplet carbene and 3O2 requires a previous singlet–triplet state crossing. The large spin-orbit coupling at this crossing suggests a rather efficient tunneling rate. This would help to explain why the rate constant in solution in these cases is only one order of magnitude smaller than those involving a spin-allowed process. Moreover, the action of the solvent as a third body appears to play a fundamental role in prompting relatively smooth rates. Figure The oxygenation of phenylhalocarbenes is predicted to be spin-allowed when the phenylhalocarbene is substituted with electron-withdrawing groups at the para position of the aromatic ring and spin-forbidden for the unsubstituted compounds, in agreement with the experimental findings.
Starting Page	2813
Ending Page	2821
Page Count	9
File Format	PDF
ISSN	16102940
Journal	Journal of Molecular Modeling
Volume Number	18
Issue Number	6
e-ISSN	09485023
Language	English
Publisher	Springer-Verlag
Publisher Date	2011-11-27
Publisher Place	Berlin, Heidelberg
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Halocarbene reactivity DFT Spin-philicity index Singlet–triplet reaction CASSCF-PT2 Computer Applications in Chemistry Computer Application in Life Sciences Life Sciences Health Informatics Molecular Medicine Biomedicine general
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Physical and Theoretical Chemistry Computational Theory and Mathematics Catalysis Inorganic Chemistry Computer Science Applications

Sl.	Authority	Responsibilities	Communication Details
1	Ministry of Education (GoI), Department of Higher Education	Sanctioning Authority	https://www.education.gov.in/ict-initiatives
2	Indian Institute of Technology Kharagpur	Host Institute of the Project: The host institute of the project is responsible for providing infrastructure support and hosting the project	https://www.iitkgp.ac.in
3	National Digital Library of India Office, Indian Institute of Technology Kharagpur	The administrative and infrastructural headquarters of the project	Dr. B. Sutradhar bsutra@ndl.gov.in
4	Project PI / Joint PI	Principal Investigator and Joint Principal Investigators of the project	Dr. B. Sutradhar bsutra@ndl.gov.in Prof. Saswat Chakrabarti will be added soon
5	Website/Portal (Helpdesk)	Queries regarding NDLI and its services	support@ndl.gov.in
6	Contents and Copyright Issues	Queries related to content curation and copyright issues	content@ndl.gov.in
7	National Digital Library of India Club (NDLI Club)	Queries related to NDLI Club formation, support, user awareness program, seminar/symposium, collaboration, social media, promotion, and outreach	clubsupport@ndl.gov.in
8	Digital Preservation Centre (DPC)	Assistance with digitizing and archiving copyright-free printed books	dpc@ndl.gov.in
9	IDR Setup or Support	Queries related to establishment and support of Institutional Digital Repository (IDR) and IDR workshops	idr@ndl.gov.in

Triplet fluoranthenes: Aromaticity versus unpaired electrons

Evaluation of the chemical reactivity in lignin precursors using the Fukui function

UV-spectroscopy, electronic structure and ozonolytic reactivity of sesquiterpenes: a theoretical study

The dual descriptor to measure local reactivity on Buckminster fullerenes: an analysis within the framework of conceptual DFT

The impact of Cu atoms on the reactivity of ZrO2 oligomers

Theoretical study of the hydrogen abstraction from vitamin-E analogues. The usefulness of DFT descriptors

Theoretical evaluation of the order of reactivity of transfer agents utilized in RAFT polymerization : Part 2: Group R

Theoretical insights into thermal cyclophanediene to dihydropyrene electrocyclic reactions; a comparative study of Woodward Hoffmann allowed and forbidden reactions

DFT and electrochemical studies on nortriptyline oxidation sites

Oxygenation of the phenylhalocarbenes. Are they spin-allowed or spin-forbidden reactions?

Similar Documents

Triplet fluoranthenes: Aromaticity versus unpaired electrons

Evaluation of the chemical reactivity in lignin precursors using the Fukui function

UV-spectroscopy, electronic structure and ozonolytic reactivity of sesquiterpenes: a theoretical study

The dual descriptor to measure local reactivity on Buckminster fullerenes: an analysis within the framework of conceptual DFT

The impact of Cu atoms on the reactivity of ZrO2 oligomers

Theoretical study of the hydrogen abstraction from vitamin-E analogues. The usefulness of DFT descriptors

Theoretical evaluation of the order of reactivity of transfer agents utilized in RAFT polymerization : Part 2: Group R

Theoretical insights into thermal cyclophanediene to dihydropyrene electrocyclic reactions; a comparative study of Woodward Hoffmann allowed and forbidden reactions

DFT and electrochemical studies on nortriptyline oxidation sites

Oxygenation of the phenylhalocarbenes. Are they spin-allowed or spin-forbidden reactions?