Dioxomolibdenum(VI) complexes with thiosemicarbazone ligands as (pre)catalysts for olefin epoxidation

master's thesis

• Title (croatian): Tiosemikarbazonski kompleksi dioksomolibdena(VI) kao (pred)katalizatori u reakcijama epoksidacije olefina
• Author: Sanja Renka
• Mentor: Višnja Vrdoljak (mentor)
• Mentor: Dominique Agustin https://orcid.org/0000-0003-1933-8442 (mentor)
• Committee member: Višnja Vrdoljak (predsjednik povjerenstva)
• Committee member: Morana Dulić (član povjerenstva)
• Committee member: Tajana Preočanin (član povjerenstva)
• Committee member: Jana Pisk (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2019-01-23, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

Three polynuclear dioxomolybdenum(VI) complexes [MoO2(5MeO-SalTSC-4-Ph)]n,
[MoO2(5MeO-SalTSC-4-Me)]n and [{MoO2(5-MeO-SalTSC)}·½CH3CN] n, two mononuclear
[MoO2(5MeO-SalTSC-4-Me)(MeOH)] and [MoO2(5MeO-SalTSC)(MeOH)]·MeOH and
hybrid organic-inorganic POM complex [MoO2(H5MeO-SalTSC-4Me)(CH3CN)]2Mo6O19
have been synthesized by the reaction of [MoO2(acac)2] and corresponding thiosemicarbazone
ligand in 1:1 and 7:1 molar ratio, respectively. Mononuclear complexes were obtained from a
methanolic solution, whereas polynuclear and POM hybrid complex from acetonitrile.
Complexes were characterized by the IR spectroscopy, elemental and thermogravimetric
analysis. Additionally, molecular and crystal structures of mononuclear complexes were
determined by the single crystal X-ray diffraction. Catalytic activity of all complexes was
tested in the solvent-free epoxidation of cis-cyclooctene, cyclohexene and (R)-limonene with
TBHP as an oxidant and low catalyst loading (0.05 %).

Abstract (croatian)

Reakcijom [MoO2(acac)2] i odgovarajućeg tiosemikarbazonskog liganda u 1:1 odnosno 1:7
molarnom omjeru pripravljeni su kompleksni spojevi molibdena(VI): polinuklearni
[MoO2(5MeO-SalTSC-4-Ph)]n, [MoO2(5MeO-SalTSC-4-Me)]n i [{MoO2(5-MeOSalTSC)
}·½CH3CN]n, mononuklearni [MoO2(5MeO-SalTSC-4-Me)(MeOH)] i
[MoO2(5MeO-SalTSC)(MeOH)]·MeOH te hibridni organsko-anorganski polioksomolibdatni
spoj [MoO2(H5MeO-SalTSC-4Me)(CH3CN)]2Mo6O19. Mononuklearni kompleksi dobiveni su
iz metanolne otopine, a polinuklearni i hibridni iz acetonitrila. Kompleksi su identificirani IR
spektroskopijom, elementnom i termogravimetrijskom analizom te je dodatno, difrakcijom
rentgenskog zračenja na monokristalnom uzorku, određena molekulska i kristalna struktura
mononuklearnih kompleksa. Katalitička aktivnost pripravljenih spojeva ispitana je u
reakcijama epoksidacije olefina (cis-ciklooktena, cikloheksena i (R)-limonena) s TBHP-om u
uvjetima bez otapala. Za epoksidaciju je korišteno 0,05 % katalizatora u odnosu na supstrat.

• Keywords: molybdenum(VI) complexes; polyoxomolybdates; solvent-free epoxidation
• Keywords (croatian): kompleksi molibdena(VI); polioksomolibdati; tiosemikarbazoni; epoksidacija bez dodatka organskog otapala
• Language: english
• URN:NBN: urn:nbn:hr:217:133616
• Study programme: Title: Graduate university studies in chemistry; specializations in: Research programme; Course: Research programme; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra kemije (magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2021-01-23
• Created on: 2019-02-04 15:09:24