Mononuklearne i polinuklearne okso vrste molibdena(VI) i vanadija(IV) s derivatima aminokiselina

doctoral thesis

• Title (english): Mononuclear and polynuclear oxo species of molybdenum(VI) andvanadium(IV) with amino acid derivatives
• Author: Gordana Vrbanec
• Mentor: Marina Cindrić (mentor)
• Committee member: Ines Primožič (predsjednik povjerenstva)
• Committee member: Marina Cindrić (član povjerenstva)
• Committee member: Gordana Pavlović (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2018-12-15, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

U okviru disertacije opisani su rezultati istraživanja reakcija okso vrsta molibdena(VI) i vanadija(IV) s
derivatima salicilaldehida i L-asparaginske kiseline, D,L-asparagina, L-glutamina te L-ornitina.
Opažena je i opisana katalitička uloga izoliranih oksomolibdatnih i oksovanadatnih vrsta u
oksidativnoj dekarboksilaciji asparagina pri čemu dolazi do nastanka kumarin-3-karboksamida i
dekavanadata, odnosno kompleksa [Mo2O4(C11H10N2O3)2], dok je u reakciji s glutaminom izoliran
sukcinamid odnosno kompleks [VO(C12H12N2O4)(OC2H5)(HOC2H5)]. U reakciji s L-ornitinom nastao
je diimin i došlo je zatvaranja piperidinskog prstena i koordinacije nastalog diimin na [MoO2]2+
kationsku vrstu. Opisana je uloga aminokiselina u reakcijama nastajanja molibdovanadatnih poliokso
vrsta. Pripravljeni su i opisani tetranuklearni molibdovanadatni kompleks [Mo2V2O9(C11H8NO5)2]2– s
derivatom salicilaldehida i L-aspartata, molibdatni anion Lindquistovog tipa, [MoVMo5
VIO19]3-,
oktamolibdati [Mo4O13(NH4)Mo4O13]n i [Mo4O13(H3O)Mo4O13]n te molibdati i molibdovanadati,
Kegginovog [BrMoV
xMoVI
(12-x)O44]n-, odnosno super-Kegginovog tipa
[BrMoV
xMoVI
13-xVIV
5VV
(5-x)O62]n-.
Pripravljeni spojevi su identificirani na osnovi rezultata kemijske analize, spektroskopskih metoda,
termičkih metoda (termogravimetrija i diferencijalna pretražna kalorimetrija) te difrakcije rentgenskih
zraka na polikristalnom i monokristalnom uzorku.

Abstract (english)

The reaction results of oxo molybdenum(VI) and vanadium(IV) species with salicylaldehidato amino
acids (L-aspartatic acid, D,L-asparagine, L-glutamine and L-ornithine) derivatives are described in the
thesis. In the reactions of molybdenum(VI) or vanadium(IV) with D,L-asparagine derivatives, the
coumarine-3-carboxamide, decavanadate and [Mo2O4(C11H10N2O3)2] were obtained. Succinamide was
obtained from the reactions with L-glutamine and dioxomolybdenum(VI), while with vanadylsulfate
mononuclear [VO(C12H12N2O4)(OC2H5)(HOC2H5)] complex was obtained. The
dioxomolybdenum(VI) complex with piperidine derivative was observed due to the diimine formation
when L-ornithine was used. Molybdovanadate reactions resulted in tetranuclear mixed complex
formation with aspartate derivative and Lindquist type molybdate [MoVMo5
VIO19]3-. Octa-
[Mo4O13(NH4)Mo4O13]n i [Mo4O13(H3O)Mo4O13]n . Keggin type molybdate [BrMoV
xMoVI
(12-x)O44]n–
and super-Keggin molybdovanadate [BrMoV
xMoVI
13-xVIV
5VV
(5-x)O62]n– were observed and
characterized. Prepared compounds were identified and characterized by means of chemical and
thermogravimetric analysis in combination with differential scanning calorimetry, spectroscopy
methods, X-ray diffraction on monocrystalline and polycrystalline samples where applicable.

• Keywords: aminokiseline; molibden(VI); polioksomolibdovanadati; polioksomolibdati; polioksovanadati; vanadij(IV)
• Keywords (english): amino acids; molybdenum(VI); molybdate; molybdovanadate; polyoxometalate; vanadium(IV)
• Language: croatian
• URN:NBN: urn:nbn:hr:217:448343
• Study programme: Title: 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 resource: Text
• Extent: 127 str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2019-12-31
• Created on: 2018-01-09 11:58:01