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Palladium and copper complexes based on dendrimeric and monofunctional N, N’ chelating ligands as potential catalysts in the oxidative carbonylation of alcoholsMketo, Nomvano 03 1900 (has links)
Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: In this thesis we describe the synthesis of several new N-(n-propyl)-1-(2-pyridyl and
quinolyl)-imine ligands (ML1-ML4) as well as peripheral functionalised iminopyridyl and
iminoquinolyl poly(propylene-imine) dendrimeric ligands (DL1-DL8) with a 1,4-
diaminobutane core. The dendrimeric ligands were obtained by modification of the
peripheral groups of Generation 1 and Generation 2 poly(propylene-imine) dendrimers,
(DAB-(NH2)n which are commercially available, with a series of aldehydes. All the ligands
were fully characterised by ESI-mass spectrometry, elemental analysis, 1H&13C{1H}-NMR,
FT-IR and UV/Vis spectroscopies.
These ligands were utilised to synthesise Pd(II) and Cu(I) complexes using appropriate metal
precursors. Some of mononuclear complexes, [N-(n-propyl)-(2-pyridyl and quinolyl)
methanimine] dichloro Pd(II) complexes (C1-C4) and bis[N-(n-propyl)-(2-pyridyl and
quinolyl) methanimine] copper(I) tetrafluoroborate complexes (C14) were structurally
characterised. Pd(II) complexes adopted a distorted square-planar geometry around the metal
centre while Cu(I) complex exhibit a distorted tetrahedral arrangement around the metal
centre. Both Pd(II) and Cu(I) multinuclear complexes (metallodendrimers) were characterised using a range of analytical techniques. / AFRIKAANSE OPSOMMING: In hierdie tesis word die sintese van verskeie nuwe N-(n-propiel)-1-(2-piridiel) en kinolielimien
ligande (ML1-ML4) sowel as gefunksioneerde imienopiridiel en imienokinoliel
poli(propilien-imien) dendrimeriese ligande (DL1-DL8) beskryf. Die dendrimeriese ligande
was behaal deur die modifikasie van perifere groepe van Generasie 1 en Generasie 2
poli(propilien-imien) dendrimere met ‘n reeks aldehiede. Alle ligande was volledig deur
ESI-massaspektrometrie, elementele analiese, 1H en 13C{1H} – KMR, FT-IR en UV/Sigbare
spektroskopie gekarakteriseerd.
Hierdie ligande was gebruik om Pd(II) en Cu(I) komplekse te berei om van die gepaste
metaal voorlopers te gebruik te maak. Sommige van die mono-kern komplekse, [N-(npropiel)-(
2-piridiel) en kinoliel metanimien] dikloor Pd(II), komplekse (C1-C4) en bis[N-(npropiel)-(
2-piridiel) metanimien] koper(I) tetrafloorboraat, kompleks (C14) was struktureël
gekarakteriseerd. Pd(II) komplekse neem ‘n versteurde vierkant valk geometrie om die
metaal senter aan, terwyl die Cu(I) kompleks, ‘n versteurde tetrahedriese opset rondom die
metaal toon.
Beide Pd(II) en Cu(I) multikern komplekse (metaaldendrimere) was deur ‘n verskeidenheid
van analitiese tegnieke gekarakteriseerd.
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