PHOSPHORUS--CARBON DIAD TAUTOMERISM IN PHOSPHONIUM COMPOUNDS. THEORETICAL STUDY.
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| Title: | PHOSPHORUS--CARBON DIAD TAUTOMERISM IN PHOSPHONIUM COMPOUNDS. THEORETICAL STUDY. |
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| Authors: | Burk, Peeter, Molder, Uldo, Tamm, Kaido |
| Source: | Proceedings of the Estonian Academy of Sciences, Chemistry. Dec2001, Vol. 50 Issue 4, p241. 13p. 5 Charts, 4 Graphs. |
| Subjects: | Tautomerism, Phosphorus, Carbonyl compounds |
| Abstract: | Phosphorus--carbon diad tautomerism was studied in phosphonium compounds with such strong electron acceptor substituents as cyano-, nitro-, fluorosulphonyl-, and trifluoromethyl-sulphonyl groups using semiempirical, ab initio, and DFT methods. It was shown that in the gas phase all studied monosubstituted species are in the phosphoryl form and no enol forms should be detectable. In contrast, for doubly substituted compounds enol forms should be well detectable and in some cases even predominant. Comparison of different calculation methods indicated that ab initio (HF/6-31 + G*) and DFT (B3LYP/6-311 + G**) calculations give close results. Both applied semiempirical methods (PM3 and MNDO/d) seem to overestimate strongly the stability of the enol form. It was also found that the MNDO/d method gives unrealistic results for compounds containing both hypervalent phosphorus and sulphur. [ABSTRACT FROM AUTHOR] |
| Copyright of Proceedings of the Estonian Academy of Sciences, Chemistry is the property of Teaduste Akadeemia Kirjastus and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Links: – Type: pdflink Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 5783102 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: PHOSPHORUS--CARBON DIAD TAUTOMERISM IN PHOSPHONIUM COMPOUNDS. THEORETICAL STUDY. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Burk%2C+Peeter%22">Burk, Peeter</searchLink><br /><searchLink fieldCode="AR" term="%22Molder%2C+Uldo%22">Molder, Uldo</searchLink><br /><searchLink fieldCode="AR" term="%22Tamm%2C+Kaido%22">Tamm, Kaido</searchLink> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Proceedings+of+the+Estonian+Academy+of+Sciences%2C+Chemistry%22">Proceedings of the Estonian Academy of Sciences, Chemistry</searchLink>. Dec2001, Vol. 50 Issue 4, p241. 13p. 5 Charts, 4 Graphs. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Tautomerism%22">Tautomerism</searchLink><br /><searchLink fieldCode="DE" term="%22Phosphorus%22">Phosphorus</searchLink><br /><searchLink fieldCode="DE" term="%22Carbonyl+compounds%22">Carbonyl compounds</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Phosphorus--carbon diad tautomerism was studied in phosphonium compounds with such strong electron acceptor substituents as cyano-, nitro-, fluorosulphonyl-, and trifluoromethyl-sulphonyl groups using semiempirical, ab initio, and DFT methods. It was shown that in the gas phase all studied monosubstituted species are in the phosphoryl form and no enol forms should be detectable. In contrast, for doubly substituted compounds enol forms should be well detectable and in some cases even predominant. Comparison of different calculation methods indicated that ab initio (HF/6-31 + G*) and DFT (B3LYP/6-311 + G**) calculations give close results. Both applied semiempirical methods (PM3 and MNDO/d) seem to overestimate strongly the stability of the enol form. It was also found that the MNDO/d method gives unrealistic results for compounds containing both hypervalent phosphorus and sulphur. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Proceedings of the Estonian Academy of Sciences, Chemistry is the property of Teaduste Akadeemia Kirjastus and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.3176/chem.2001.4.06 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 13 StartPage: 241 Subjects: – SubjectFull: Tautomerism Type: general – SubjectFull: Phosphorus Type: general – SubjectFull: Carbonyl compounds Type: general Titles: – TitleFull: PHOSPHORUS--CARBON DIAD TAUTOMERISM IN PHOSPHONIUM COMPOUNDS. THEORETICAL STUDY. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Burk, Peeter – PersonEntity: Name: NameFull: Molder, Uldo – PersonEntity: Name: NameFull: Tamm, Kaido IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 12 Text: Dec2001 Type: published Y: 2001 Identifiers: – Type: issn-print Value: 14060124 Numbering: – Type: volume Value: 50 – Type: issue Value: 4 Titles: – TitleFull: Proceedings of the Estonian Academy of Sciences, Chemistry Type: main |
| ResultId | 1 |
