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doctoral thesis
Elektrofugalnost fenilferocenilmetilnih kationa
Zagreb: University of Zagreb, Faculty of Science, 2020. urn:nbn:hr:217:139397
Marijan, Marijan
University of Zagreb
Faculty of Science
Department of Chemistry

Institutional repository: Repository of the Faculty of Science

Cite this document

Marijan, M. (2020). Elektrofugalnost fenilferocenilmetilnih kationa (Doctoral thesis). Zagreb: University of Zagreb, Faculty of Science. Retrieved from https://urn.nsk.hr/urn:nbn:hr:217:139397

Marijan, Marijan. "Elektrofugalnost fenilferocenilmetilnih kationa." Doctoral thesis, University of Zagreb, Faculty of Science, 2020. https://urn.nsk.hr/urn:nbn:hr:217:139397

Marijan, Marijan. "Elektrofugalnost fenilferocenilmetilnih kationa." Doctoral thesis, University of Zagreb, Faculty of Science, 2020. https://urn.nsk.hr/urn:nbn:hr:217:139397

Marijan, M. (2020). 'Elektrofugalnost fenilferocenilmetilnih kationa', Doctoral thesis, University of Zagreb, Faculty of Science, accessed 27 December 2024, https://urn.nsk.hr/urn:nbn:hr:217:139397

Marijan M. Elektrofugalnost fenilferocenilmetilnih kationa [Doctoral thesis]. Zagreb: University of Zagreb, Faculty of Science; 2020 [cited 2024 December 27] Available at: https://urn.nsk.hr/urn:nbn:hr:217:139397

M. Marijan, "Elektrofugalnost fenilferocenilmetilnih kationa", Doctoral thesis, University of Zagreb, Faculty of Science, Zagreb, 2020. Available at: https://urn.nsk.hr/urn:nbn:hr:217:139397

Metadata
TitleElektrofugalnost fenilferocenilmetilnih kationa
Title (english)Electrofugality of ferrocenylpheylmethyl cations
AuthorMarijan Marijan
MentorSandra Jurić (mentor)
Committee memberInes Primožič (predsjednik povjerenstva)
Committee memberOlga Kronja (član povjerenstva)
Committee memberIvan Kodrin (član povjerenstva)
GranterUniversity of Zagreb
Faculty of Science
(Department of Chemistry)
Zagreb
Defense date and country2020-06-29, Croatia
Scientific / art field,
discipline and subdiscipline		NATURAL SCIENCES
Chemistry
Universal decimal classification
(UDC)		54 - Chemistry. Crystallography. Mineralogy
Abstract
Određivanje solvolitičke reaktivnosti niza različito supstituiranih fenilferocenilmetilnih karboksilata korištenjem LFER jednadžbe kako bi se odredila mogućnost fenilferocenilmetilnih kationa da napuste supstrat, tj. njihova elektrofugalnost, bio je glavni cilj ove doktorske disertacije. Određena je elektrofugalnost derivata raznih fenilferocenimetilnih kationa upotrebom ljestvice elektrofugalnosti i nukleofugalnosti koja se temelji na solvolitičkoj reaktivnosti različitih benzhidrilnih derivata u različitim otapalima. Prema tom pristupu se konstanta heterolize nekog supstrata može prikazati i predvidjeti kao linearna kombinacija triju faktora u LFER jednadžbi log k = sf (Nf + Ef) gdje je k konstanta brzine reakcije prvog reda pri 25 °C, sf predstavlja nagib pravca i vezan je za nukleofugalnost, Nf je nukleofugalnost u zadanom otapalu te Ef nezavisni parametar elektrofugalnosti. Kinetička mjerenja su pokazala da prisutnost ferocenilne skupine u α-položaju s obzirom na reakcijski centar povećava reaktivnost supstrata u solvolitičkim reakcijama koje se odvijaju SN1 mehanizmom za oko 8 redova veličine u odnosu na benzhidrilne derivate te stabilizira nastali kation delokalizacijom naboja na atom željeza. Parametri elektrofugalnosti za fenilferocenilmetilne katione uspoređeni su s literaturno dostupnim Ef vrijednostima slično supstituiranih kationa.
Abstract (english)
The main aim of this dissertation was to examined the solvolytic behavior of the series of ferrocenylphenylmethyl carboxylates using LFER equation and by determining the abilities of the ferrocenylphenylmethyl cations to leave the substrate, i.e., by defining their electrofugality.The electrofugality of 11 ferrocenylphenylmethyl cation derivatives with different substituents was determined by using an electrofugality and nucleofugality scale based on the solvolytic reactivity of different benzhydryl derivatives in different solvents. Accordingly, the heterolysis rate constant of any substrate in a given solvent can be predicted by using the following three-parameter LFER equation log k = sf (Nf + Ef) in which k is first-order rate constant at 25 °C, sf is the nucleofuge-specific slope parameter, Nf is the nucleofugality in a given solvent, and Ef is the independent variable referring to electrofugality. Kinetic studies established that the ferrocenyl group (Fc) in α-position to the reaction center enhances the SN1 solvolytic reactivity of the supstrate for almost 8 orders of magnitude. Also, stabilizing effect of the ferrocenyl group in comporation with that of less reactive substrates were examined to make feasible comparison of reactivities of the series of ferrocenylphenylmethyl cations with numerous electrofuges with known Ef values.
Keywords
Keywords (english)
Languagecroatian
URN:NBNurn:nbn:hr:217:139397
Promotion2020
Study programmeTitle: Doctoral study in chemistry
Study programme type: university
Study level: postgraduate
Academic / professional title: doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija (doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija)
Type of resourceText
Extent135 str. ; 30 cm
File originBorn digital
Access conditionsOpen access
Terms of useLicence In copyright icon
Created on2020-07-16 10:33:43