8/9/2017 Web of Science [v.5.25.1] - Web of Science Core Collection Full Record
http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=3&SID=2AK2ui7C17SC59MSMlQ&page=8&doc=… 1/2
Tautomerization, acidity, basicity, and stability of cyanoform: a computational study
By:Elroby, SA (Elroby, Shaaban A.)[ 1,2 ] View ResearcherID and ORCID
CHEMISTRY CENTRAL JOURNAL Volume: 10
Article Number: 20
DOI: 10.1186/s13065-016-0166-z Published: APR 11 2016 View Journal Impact
Abstract
Background: Cyanoform is long known as one of the strongest acid. Cyanoform is only stable below -40 degrees C. The issue of the stability and tautomeric equilibria of cyanoform (CF) are investigated at the DFT and MP2 levels of theory. The present work presents a detailed study of structural tautomer interconversion in three different media, namely, in the gas phase, in a solvent continuum, and in a microhydrated environment where the first solvation layer is described explicitly by one or two water molecule. In all cases, the transition state has been localized and identified. Proton affinities, deprotonation energies and the Raman spectra are reported analyzed and discussed.
Results: The 1 tautomer of cyanoform is shown to be more stable than 2 form by only 1.8 and 14.1 kcal/mol in the gas phase using B3LYP/6-311++G** and MP2/6-311++G** level of theory, respectively.
This energy difference is reduced to 0.7 and 13.4 kcal/mol in water as a solvent using CPCM model using B3LYP/6-311++G** and MP2/6-311++G** level of theory, respectively. The potential energy barrier for this proton transfer process in the gas phase is 77.5 kcal/mol at MP2/6-311++G** level of theory. NBO analysis, analysis of the electrostatic potential (ESP) of the charge distribution, donor- acceptor interactions and charge transfer interactions in 1 and 2 are performed and discussed.
Conclusions: Gross solvent continuum effects have but negligible effect on this barrier. Inclusion of one and two water molecules to describe explicitly the first solvation layer, within the supermolecule model, lowers the barrier considerably (29.0 and 7.6 kcal/mol, respectively). Natural bond orbital (NBO) analysis indicated that the stability of the cyanoform arising from charge delocalization. A very good agreement between experimental and theoretical data has been found at MP2/6-311++G** for the energies. On other hand, B3LYP/6-311++G** level of theory has good agreement with experimental spectra for CF compound.
Keywords
Author Keywords:Cyanoform; Tautomerization; Water-assisted proton transfer; B3LYP; MP2; PCM;
Raman spectra
KeyWords Plus:DENSITY-FUNCTIONAL THERMOCHEMISTRY; POTASSIUM CYANIDE; PROTON- TRANSFER; IR-SPECTRA; BASIS-SET; FREQUENCIES; B3LYP
Author Information
Reprint Address: Elroby, SA (reprint author)
King Abdulaziz Univ, Fac Sci, Dept Chem, POB 80203, Jeddah 21589, Saudi Arabia.
Organization-Enhanced Name(s) King Abdulaziz University
Citation Network
0
Times Cited 43 Cited References View Related RecordsCreate Citation Alert (data from Web of Science Core Collection)
All Times Cited Counts 0 in All Databases
0 in Web of Science Core Collection 0 in BIOSIS Citation Index 0 in Chinese Science Citation Database
0 in Data Citation Index
0 in Russian Science Citation Index 0 in SciELO Citation Index
Usage Count Last 180 Days: 1 Since 2013: 9 Learn more
This record is from:
Web of Science Core Collection - Science Citation Index Expanded
Suggest a correction
If you would like to improve the quality of the data in this record, please suggest a correction.
Web of Science InCites Journal Citation Reports Essential Science Indicators EndNote Publons Sign In Help English
My Tools Search History Marked List
Look Up Full Text Add to Marked List
Full Text Options Save to EndNote online
391 of 752 Search Search Results
Web of Science
8/9/2017 Web of Science [v.5.25.1] - Web of Science Core Collection Full Record
http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=3&SID=2AK2ui7C17SC59MSMlQ&page=8&doc=… 2/2 Addresses:
[ 1 ] King Abdulaziz Univ, Fac Sci, Dept Chem, POB 80203, Jeddah 21589, Saudi Arabia Organization-Enhanced Name(s)
King Abdulaziz University
[ 2 ] Beni Suef Univ, Dept Chem, Fac Sci, Bani Suwayf 62511, Egypt E-mail Addresses:[email protected]
Publisher
BIOMED CENTRAL LTD, 236 GRAYS INN RD, FLOOR 6, LONDON WC1X 8HL, ENGLAND
Categories / Classification
Research Areas: ChemistryWeb of Science Categories: Chemistry, Multidisciplinary
Document Information
Document Type: Article Language: EnglishAccession Number: WOS:000374741300001 PubMed ID: 27073411
ISSN: 1752-153X
Journal Information
Impact Factor: Journal Citation Reports
Other Information
IDS Number: DK2JRCited References in Web of Science Core Collection: 43 Times Cited in Web of Science Core Collection: 0
391 of 752
© 2017 CLARIVATE ANALYTICS TERMS OF USE PRIVACY POLICY FEEDBACK
