Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-28T11:08:11Z | - |
dc.date.available | 2016-08-28T11:08:11Z | - |
dc.date.issued | 2009 | - |
dc.identifier.issn | 0253-2964 | - |
dc.identifier.other | OAK-13365 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/229372 | - |
dc.description.abstract | Second-order rate constants (kHOO-) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted phenyl benzenesulfonates (1a-g) with HOO- ion in H2O at 25.0 ± 0.1 °C. The Brønsted-type plot is linear with βlg = -0.73. The Hammett plot correlated with with σ- constants results in much better linearity than σo constants, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS) either in a stepwise mechanism or in a concerted pathway. However, a stepwise mechanism in which departure of the leaving group occurs in the RDS has been excluded since HOO- ion is more basic and a poorer leaving group than the leaving Y-substituted phenoxide ions. Thus, the reactions of 1a-g with HOO- ion have been concluded to proceed through a concerted mechanism. The α-nucleophile HOO- ion is more reactive than its reference nucleophile OH- ion although the former is ca. 4 pKa units less basic than the latter (i.e., the α-effect). TS stabilization through intramolecular H-bonding interaction has been suggested to be irresponsible for the α-effect shown by HOO- ion, since the magnitude of the α-effect is independent of the electronic nature of substituent Y in the leaving group. GS destabilization through desolvation of HOO- ion has been concluded to be responsible for the α-effect found in the this study. | - |
dc.language | English | - |
dc.title | The α-effect and mechanism of reactions of Y-substituted phenyl benzenesulfonates with hydrogen peroxide ion | - |
dc.type | Article | - |
dc.relation.issue | 10 | - |
dc.relation.volume | 30 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.index | KCI | - |
dc.relation.startpage | 2393 | - |
dc.relation.lastpage | 2397 | - |
dc.relation.journaltitle | Bulletin of the Korean Chemical Society | - |
dc.identifier.doi | 10.5012/bkcs.2009.30.10.2393 | - |
dc.identifier.wosid | WOS:000271556300041 | - |
dc.identifier.scopusid | 2-s2.0-75849148333 | - |
dc.author.google | Im L.-R. | - |
dc.author.google | Um I.-H. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |