Pregled bibliografske jedinice broj: 891268
Solvolytic Reactivity of Organic Phosphates
Solvolytic Reactivity of Organic Phosphates // European Symposium on Organic Reactivity 2017 - Book of abstracts / O`Donoghue, A. C. ; Hodgson, D. R. W. (ur.).
Durham (NC), 2017. str. PP23-PP23 (poster, nije recenziran, sažetak, znanstveni)
CROSBI ID: 891268 Za ispravke kontaktirajte CROSBI podršku putem web obrasca
Naslov
Solvolytic Reactivity of Organic Phosphates
Autori
Matić, Mirela ; Denegri, Bernard ; Byrne, Peter ; Kronja, Olga ; Mayr, Herbert
Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni
Izvornik
European Symposium on Organic Reactivity 2017 - Book of abstracts
/ O`Donoghue, A. C. ; Hodgson, D. R. W. - Durham (NC), 2017, PP23-PP23
Skup
European Symposium on Organic Reactivity
Mjesto i datum
Durham, Ujedinjeno Kraljevstvo, 03.09.2017. - 08.09.2017
Vrsta sudjelovanja
Poster
Vrsta recenzije
Nije recenziran
Ključne riječi
organic phosphates ; nucleofugalities ; negative hyperconjugation
Sažetak
Heterolytic reactivities (nucleofugalities) of some organic phosphate leaving groups have been determined in terms of Nf parameters from solvolysis rate constants of corresponding benzhydryl derivatives according to equation log k (25 °C) = sf(Ef + Nf)(1).In this fashion, the nucleofugality of organic phosphates can be compared with nucleofugalities of numerous leaving groups in a wide range of reactivity in the existing nucleofugality scale. Nf values can further be used for estimating the heterolytic reactivity of various substrates according to equation (1). It was previously established that the negative hyperconjugation is operative in heterolytic transition states of carbonate diesters as well as in free aryl/alkyl carbonate anions, transferring electron density out of the carboxylate moiety. The difference in heterolytic reactivity between diphenyl phosphate and dimethyl phosphate leaving groups of even two orders of magnitude indicates that additional orbital effects exist in both heterolytic transition states and corresponding free phosphate anions since a direct transfer of the anionic charge to the aromatic rings of diphenyl phosphate is not possible. In order to investigate stabilizing effects that occur in leaving groups along the heterolytic reaction coordinate of phosphates, quantum chemical calculations have been employed.
Izvorni jezik
Engleski
Znanstvena područja
Kemija
POVEZANOST RADA
Projekti:
HRZZ-IP-2013-11-1021 - STRUKTURNA OBILJEŽJA KOJA ODREĐUJU NUKLEOFUGALNOST IZLAZNIH SKUPINA TE TEORIJSKI MODEL ZA PROCJENU SOLVOLITIČKE REAKTIVNOSTI (NUCLEOFUGALITY) (Kronja, Olga, HRZZ - 2013-11) ( CroRIS)
Ustanove:
Farmaceutsko-biokemijski fakultet, Zagreb
