The research conducted in this study focussed on advancing the knowledge database of diamineplatinum complexes on two frontiers: 1) the development of novel anticancer complexes, and 2) improvements in their synthetic chemistry. Novel square-planar dichloro and oxalato platinum(II) complexes were synthesized as potential anticancer agents in accordance with a comprehensive set of factors identified as being significant in optimizing such action. The nonleaving ligands consisted of asymmetric chelating chiral diamines of the form 1- (1-R-imidazol-2yl)(R')methanamine (R representing methyl, butyl and R' methyl, phenyl). The complexes were characterized by a host of spectral, thermal and crystallographic techniques. In addition, the stabilities of the complexes were monitored in aqueous and saline solutions. Cytotoxicity screening on three cultured cancer cell lines (MCF-7, HeLa and HT29) indicated the compounds, present as their respective racemates, to have rather modest activities relative to cisplatin; with complexes having the smallest substituents, R,R' = methyl, being most active. In recognition of the limitations of traditional silver-based syntheses of oxalatoplatinum(II) complexes, innovative non-silver methods were developed using the well known cancer drug, oxaliplatin, (trans-R,R-1,2- diaminocyclohexane)oxalatoplatinum(II), as a prototype. These involved direct ligand exchange reactions of the dichloro precursor, (trans-R,R-1,2- diaminocyclohexane)dichloroplatinum(II), with tetrabutylammonium oxalate in essentially non-aqueous solvents. A 90:10 mixture of isoamyl alcohol (3-methyl- 1-butanol):water, proved to be a promising solvent, enabling the recovery of pure oxaliplatin (~98 percent) after 9 hours at 88 °C in yields of up to 86 percent. In light of the perceived unique mode of anticancer action available to mononitroplatinum(IV) complexes (i.e. their STAT3-binding potential), octahedral diamineoxalatoplatinum(IV) complexes containing axially-coordinated nitro and halo co-ligands were synthesized and extensively characterized. Electrochemical studies revealed trends in reduction potential which could be correlated to structural / chemical traits of the coordinated diamine and axial ligands. The similarities of the determined cytotoxicities of the platinum(IV) compounds and their respective platinum(II) analogues, implicated reduction as a means of activation of the platinum(IV) complexes.

pK_n values for step-wise dissociation of protons from the protonated ligands (glycine, α-amino isobutyric acid, sarcosine and theonine) were determined potentiometrically with a Beckman Model GS pH meter in aqueous solution at 10, 20, 30 and 40° C. Log K values for step-wise interaction of glycine, α-amino isobutyric acid, sarcosine and threonine with copper(II) ion were also determined potentiometrically with a pH meter at 10, 20, 30 and 40° C. The standard free energy of formation for the step-wise interaction of copper(II) with each of the above ligands was calculated from the values of log K. Enthalpy and entropy changes were calculated for each of the above reactions at 20° C. Measurements of pH were obtained at several ionic strengths for each metal io-ligand system at each temperature. It was assumed that the zwitterion has no charge. The hydrolysis of copper(II) ion and the liquid junction potential were assumed to be negligible. Log K_1 and log K_2 values for the copper(II) chelate of α-amino isobutyric acid are lower than those of glycine at 10 20° C. but higher at 30 and 40° C. This may be related to the positive inductive effect and the steric effect of methyl groups. The large decrease in the log K values of the copper(II) chelate of sarcosine is probably due to two effects, namely, steric and hydration. These two effects counteract the positive inductive effect introduced by the methyl group on the nitrogen and actually decrease its basic strength and thus decrease the bond strength between nitrogen and copper. THe decrease in the log K values of the copper (II) chelate of threonine is explained by the presence of the hydroxyl group which increases the acid strength of the NH_3^+ group and decreases its electron donating power. This is probably due to the hydrogen bonding between the hydrogen of the hydroxyl group and nitrogen of the amino group. Values of log K for the copper(II) chelate of each ligand decrease with the increase in the temperature, indicating that the entropy effect is greater at a lower temperature than at a higher temperature. Calculations of n, [A^-] and log K were carried out on an IBM 650 Computer.

The object of the research was to study, by means of ion-exchange chromatography, the product mixture resulting from reaction of trans-[Co(en)₂Cl₂]Cl and SCN¬⁻. Cis-and trans-[Co(en)₂(NCS)Cl]Cl had previously been obtained as products of this reaction. However, the possibility of the presence of other products consistent with the nature of the reactants could not be dismissed. These include the dichlora, dithiocyanato, and aqua complexes. The constituents of the solution resulting from the reaction were separated on a column of Dowex 50W-X8 resin by elution with hydrochloric acid. The eluted fractions were evaporated at room temperature in order to obtain crysta1s to be used for infrared spectral analysis and identification. Three primary fractions were eluted from the column. The first, eluted with 0.5 M HCl, was identified as trans-[Co(en)₂(NCS)Cl]Cl by analysis of the infrared spectrum. Two types of crystals were obtained from the second fraction which was eluted with 1 M HCL. The first crystals to form in this solution were orange in color and were identified by examination of the infrared spectrum as cis-[Co(en)₂(NCS)Cl]Cl. The second crystals obtained from the same fraction were shown to be cis-[Co(en)₂(NCS)Cl]Cl. The crystals isolated from the third fraction, eluted with 3 M¬¬ HCl, were also identified as cis [Co(en)₂(NCS) Cl]Cl. On the basis of observations of the column elution and an analysis of the ultraviolet spectra of’ the eluted fractions, it was concluded that band #2 was cis-[Co(en)₂(NCS)Cl] Cl and band #3 was cis-[Co(en)₂(NCS)(H₂0)]Cl₂. Aquation of cis-[Co(en)₂(NCS)Cl]⁺ was observed to occur on the column as well as in the eluted solution. In addition, rechlorination of the aquated compound was found to occur in the eluted fraction so that after elution the second and third fractions were mixtures of the unaquated and aquated complexes. No crystals of dithiocyanato or dichloro compounds were obtained in the separation so that the reaction was demonstrated to be essentially1:1 between the complex and thiocyanate. Trans-[Co(en)₂(NCS)Cl]Cl was found to comprise forty-nine percent of the typical product mixture. Since other products were present only in very low concentrations, the combined cis-[Co(en)₂(NCS)Cl]Cl and cis-[Co(en)₂(NCS)(H₂0)]Cl₂ contents was estimated at roughly fifty mole percent.

No description available.

Este trabalho descreve a síntese e a caracterização de compostos de coordenação formados a partir do sal nitrato de uranilo hexaidratado e os ligantes piridina-N-áxido e suas três formas isoméricas derivadas (2-picolina-N-áxido, 3-picolina-N-óxido e 4-picolina-N-óxido).. Os complexos foram preparados a partir da reação do sal nitrato de uranilo hexaidratado com os aminóxidos aromáticos em meio etanólico, na proporção 1:2. Os compostos foram caracterizados por análise elementar (CHN), espectroscopia de absorção na região do infravermelho, difração de raios x pelo método do pó, termogravimetrialtermogravimetria derivada (TG/DTG), calorimetria exploratória diferencial (DSC), testes de solubilidade e espectroscopia de emissão na região do visível. Os compostos foram isolados na forma sólida, apresentam coloração amarelada e são praticamente insolúveis na maioria dos solventes. Os resultados analíticos sugerem fórmula geral UO2(NO3)2.2L e as curvas TG/DTG e DSC permitiram avaliar o comportamento térmico dos complexos. Os espectros de absorção no infravermelho indicam que os complexos foram isolados na forma anidra e que a coordenação do ligante ocorre através do oxigênio do grupo NO, Os difratogramas de raios x pelo método do pó não indicam a presença de isomorfismo entre os compostos.As curvas TG/DTG permitiram inferir que o composto UO2(NO3)2.2(pyO) é o mais estáveL As curvas DSC evidenciam o processo de fusão no início da decomposição térmica dos complexos. O produto final corresponde a uma mistura de UO3 e U3O8 como produto final. / The synthesis and characterization of complexes or uranyl nitrate with pyridine-N-oxide and the three derivatives isomeric forms (2-picolíne- N-oxide, 3-picoline-N-oxide and 4-picoline-N-oxide) as ligands are described. They were prepared by reaction of hydrated uranyl nitrate with ligands in ethanolic solution (mo1ar ratio 1:2). The compounds were characterized by CHN microanalyticalprocedures, infrared spectroscopy, x ray power diffraction, TG/DTG and emission spectroscopy. The analytical results suggest de general fornula UO2(NO3)2.2L and the NO group oxygen. X ray power difracttion pattems do not indicate the presence of isomphism for this series of compounds. The the compounds have luminescence and the thermal decomposition yield a mixture of UO2 and U3O8 as final product.

Este trabalho descreve a síntese e a caracterização de compostos de coordenação formados a partir do sal nitrato de uranilo hexaidratado e os ligantes piridina-N-áxido e suas três formas isoméricas derivadas (2-picolina-N-áxido, 3-picolina-N-óxido e 4-picolina-N-óxido).. Os complexos foram preparados a partir da reação do sal nitrato de uranilo hexaidratado com os aminóxidos aromáticos em meio etanólico, na proporção 1:2. Os compostos foram caracterizados por análise elementar (CHN), espectroscopia de absorção na região do infravermelho, difração de raios x pelo método do pó, termogravimetrialtermogravimetria derivada (TG/DTG), calorimetria exploratória diferencial (DSC), testes de solubilidade e espectroscopia de emissão na região do visível. Os compostos foram isolados na forma sólida, apresentam coloração amarelada e são praticamente insolúveis na maioria dos solventes. Os resultados analíticos sugerem fórmula geral UO2(NO3)2.2L e as curvas TG/DTG e DSC permitiram avaliar o comportamento térmico dos complexos. Os espectros de absorção no infravermelho indicam que os complexos foram isolados na forma anidra e que a coordenação do ligante ocorre através do oxigênio do grupo NO, Os difratogramas de raios x pelo método do pó não indicam a presença de isomorfismo entre os compostos.As curvas TG/DTG permitiram inferir que o composto UO2(NO3)2.2(pyO) é o mais estáveL As curvas DSC evidenciam o processo de fusão no início da decomposição térmica dos complexos. O produto final corresponde a uma mistura de UO3 e U3O8 como produto final. / The synthesis and characterization of complexes or uranyl nitrate with pyridine-N-oxide and the three derivatives isomeric forms (2-picolíne- N-oxide, 3-picoline-N-oxide and 4-picoline-N-oxide) as ligands are described. They were prepared by reaction of hydrated uranyl nitrate with ligands in ethanolic solution (mo1ar ratio 1:2). The compounds were characterized by CHN microanalyticalprocedures, infrared spectroscopy, x ray power diffraction, TG/DTG and emission spectroscopy. The analytical results suggest de general fornula UO2(NO3)2.2L and the NO group oxygen. X ray power difracttion pattems do not indicate the presence of isomphism for this series of compounds. The the compounds have luminescence and the thermal decomposition yield a mixture of UO2 and U3O8 as final product.

Thesis (MSc)--Stellenbosch University, 2003. / ENGLISH ABSTRACT: Advances in pharmacology, biochemistry and biotechnology are increasingly dependant upon affinity chromatography as a preferred separation technique for the purification and characterisation of specific biomolecules. In the past few years avidin-biotin technology has been widely and successfully used in the fields of medicine, pharmacy, biology and biochemistry. The avidin-biotin complex (ABC) has been used as a mediator for affinity chromatography, affinity cytochemistry, immunoassay, histopathology, bioaffinity sensors, erosslinking and immobilisation studies. The main reason for the popularity of the ABC and its growing usefulness in biotechnology is the exceptionally high affinity (1015 M-l) and stability of the noncovalent interaction between avidin and biotin. The use of the ABC is broadening as different biotin derivatives and avidin-containing conjugates are becoming commercially available. The aim of this work was to evaluate the usefulness of a plutonic" FI 08 and the ABC conjugate to effect affinity separation. Towards this aim, the adsorption of plutonic" F108 onto hydrophobic polysulphone membrane surfaces was studied. This information was used to determine the theoretical maximum amount of pluronic" FI08 that will adsorb onto a unit surface area of the membrane. It is known that the polypropylene oxide (PPO) centre block ofthe pluronic" F I08 surfactant molecule governs the concentration of pluronic" F I 08 molecules that will adsorb onto a given hydrophobic surface. If the maximum coating concentration of plutonic" FI08 is known, one can assume that the maximum coating concentration of any pluronic derivative, with the same PPO centre block size, will be the same. Adsorption studies were carried out, the Langmuir adsorption isotherm was determined, and subsequently the fractional coating was calculated. The end-groups of plutonic" FI08 were modified as follows and the substituted pluronic was adsorbed onto a membrane that was to act as the solid support matrix in the development of an affinity system: Amino pluronic was synthesised by first tosylating pluronic" FI08, followed by azidation with NaN3 then reduction with LiAI~. The synthesised amino pluronic was then biotinylated using N-hydroxysuccinimide biotin ester. The suitability of this synthetic route was first assessed on a model compound, 2-methoxyethylamine, and validated by NMR (Nuclear Magnetic Resonance) spectroscopy. The synthetic protocol was then used to derivatise the larger pluronic molecule. The affinity system was tested on two different hydrophobic surfaces: polystyrene and polysulphone membranes (PSMs). Avidin-conjugated horseradish peroxidase was obtained and used to interact with the immobilised biotin. The enzymatic reaction of the coupled peroxidase converted the substrate, 2, 2'-azino-di-(3-ethyl-benzthiazoline-6-sulphonic acid) (ABTS) to a coloured product. The colour developed is proportional to the amount of biotin that was immobilised on the hydrophobic surfaces studied. Non-covalent immobilisation of the synthesised biotin-pluronic molecule was successfully obtained onto the hydrophobic polystyrene as well as the polysulphone membrane surfaces. / AFRIKAANSE OPSOMMING: Vooruitgang in die farmakologie, biochemie en biotegnologie word al meer afhanklik van affiniteits chromatografie as die verkose tegniek vir die suiwering en karaterisering van spesifieke biomolekules. Oor die afgelope jare het die avidien-biotien tegnologie homself as baie bruikbaar bewys in die mediese, farmakologiese, biologiese en biochemiese velde. Toepassings waar die avidien-biotien kompleks betrokke was sluit in die toepassing as 'n mediator vir affiniteits chromatografie, affiniteits sitologie, immuno bepalings, histopatologie, bioaffiniteits sensors sowel as kruisbinding en immobiliserings studies en vele meer. Die hoofrede vir die gewildheid van die avidien-biotien kompleks en die groeiende bruikbaarheid in die biotegnologie is die buitengewone hoë affiniteit (l015 M-I ) en stabiliteit van die nie-kovalente interaksie tussen avidien en biotien. Die toepassingsveld van die avidien-biotien kompleks word wyer met die verskeidenheid biotien derivate en avidien-bevattende konjugate wat kommersiëel beskikbaar is. Die doel van die werk wat hier gedokumenteer word is om die bruikbaarheid van Plutonic" FI08 en die avidien-biotien kompleks, vir gebruik in 'n affiniteits chromatografie sisteem, te evalueer. Om hierdie doel te bereik is die adsorpsie van Pluronic" FI08 aan hidrofobiese polisulfoon membraan oppervlaktes bestudeer. Die eksperimentele data wat gegenireer is, is gebruik om die teoretiese maksimum hoeveelheid Pluronic wat per eenheids oppervlakte membraan adsorbeer te bepaal. Dit is reeds bekend dat die polipropileen (PPO) middel blok van die Pluronic emulgant die konsentrasie van die geadsorbeerde Pluronic molekules op 'n gegewe hidrofobiese oppervlakte bepaal. Indien die maksimum bedekkingskonsentrasie VIr maksimum oppervlakbedekking van Plutonic" FI08 bekend is, kan teoreties aanvaar word dat die bedekkingskonsentrasie vir enige Pluronic derivaat met dieselfde grootte PPO blok dieselfde sal wees. Adsorpsiestudies was uitgevoer om die Langmuir adsorpsie isoterm te bepaal. Daaropvolgend was die fraksionele bedekking bereken. Amino-pluronic was gesintetiseer deur die eindpunte van Pluronic te derivatiseer. Hierdie Pluronic derivaat was gevolglik geadsorbeer aan 'n membraan wat gedien het as die soliede oppervlakte vir die ontwikkeling van 'n affiniteits chromatografie sisteem. Amino-pluronic was gesintetiseer deur Pluronic eers te tosileer en daarna te asideer met NaN3 en laastens te reduseer met LiAI~. Die produk was gebiotinileer deur gebruik te maak van N-hidroksisuksinimied-biotien-ester. Die bruikbaarheid van hierdie sintetiese roete is eers bepaal deur van 'n model verbinding, 2-metoksiëtielamien, gebruik te maak en dit met behulp van KMR (Kern Magnetiese Resonans) spektroskopie te karakteriseer. Die affiniteits sisteem is getoets op twee verskillende hidrofobiese oppervlaktes naamlik polistireen en polisulfoon membraan oppervlaktes. Avidien gekonjugeerd met 'n peroksiedase ensiem is gebruik om met die geïmmobiliseerde biotien te assosieer. Die ensiematiese reaksie van die gekoppelde peroksiedase het die substraat 2, 2' -azino-di-(3-etiel-benzthiazolien-6-sulfoonsuur) (ABTS) omgesit na 'n gekleurde produk, waar dit teenwoordig is. 'n Reeks wasstappe is gebruik om die gemodifiseerde peroksidase ensiem wat nie aan die hidrofobiese oppervlakte gekoppel nie, weg te spoel. Hierdeur is die mate van binding aan die hirofobiese oppervlakte gekwantifiseer deur die kleur te kwantifiseer wat ontwikkelomdat die kleurontwikkeling direk proporsioneel is aan die hoeveelheid peroksidase wat nog aan die membraan gekoppel is. Nie-kovalente immobilisasie van die gesintetiseerde biotien-pluronic molekule is suksesvolop beide die hidrofobiese polistireen oppervlakte sowel as die polisulfoon membraan verkry.

Thesis (MSc)--Stellenbosch University, 2003. / ENGLISH ABSTRACT: In this study, a number of mono- and di-substituted acyl(aroyl)thioureas were investigated for potential application as specific carriers (ionophores) for the transport and extraction of Ag(l) from a mixture of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(lI) ions. The experimental arrangement for the transport experiments employed a liquid membrane set up involving a 3-phase system - 2 aqueous phases (source and receiving phase) separated by a chloroform membrane incorporating the ligand. Competitive metal ion transport experiments were conducted using the liquid membrane set up. The aqueous source and receiving phases were analyzed using Atomic Absorption Spectroscopy (AAS) and results were confirmed by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICPOES). The transport results show that the N,N-dialkyl-substituted-N'-acyl(aroyl) (HL) thioureas studied, with the exception of the N,N-di-(2-hydroxyethyl)-N'-benzoylthiourea (HL3 ) and N-piperidyl-N'-4-nitrobenzoylthiourea (HL9 ), were efficient and selective for Ag(I). HL9 was also selective for Ag(l) but not efficient. HL3 was selective for Cu(II). Under the experimental conditions employed, 13% Cu(lI) was transported by HL3 . Among the N,Ndialkyl- N'-aroylthioureas, maximum Ag(l) transport was obtained by using N,N-diethyl-N'-4- chlorobenzoylthiourea (HL5 ) and N,N-di-n-butyl-N'-benzoylthiourea (HL \ Under the experimental conditions employed, the percentages of Ag(l) transported by HL5 and HL 1 were 48% and 42% respectively. The transport selectivity and efficiency of 3,3,3' ,3'-tetraethyl-1 ,1'-isophthaloylbisthiourea (H2L12 ) and N,N-diethyl-N'-camphanoylthiourea (HL13)for Ag(l) were also studied. We were particularly interested, in comparing the Ag(l) transport and extraction efficiency of these ligands with that of the HL and H2L ligands. The experimental results reveal that, of all the ligands we investigated in this study, HL 13 was the most efficient and selective carrier for Ag(l) transport. The interesting result is that, depending on the ligand concentration used, HL 13 transported 71-81% of Ag(I). Competitive two-phase metal ion solvent extraction experiments were also performed under conditions similar to the transport studies. The results show that by varying the ligand concentration in the membrane phase, up to 100% Ag(l) can be selectively and efficiently extracted from the mixture of the seven metal ions. Finally, the N,N-di-(n)-butyl-N'-benzoylthiourea (HL1) ligand and its complex with Ag(l) were synthesized. Single crystals of the complex were grown for X-ray crystallography and the crystal and molecular structure of the complex was determined. The crystal structure showed that Ag(l) is bonded to the deprotonated ligand through the S,O atoms forming interesting cluster [Ag (L - S, 0)] 4 in the solid state. This structure is monoclinic and crystallizes in the space group P21!c with a = 17.805 (4) A, b = 21.759 (4) A, c = 36.438 (7) A, f3= 96.34(3)°, Z = 8 and a final R-factor of 5.4%. / AFRIKAANSE OPSOMMING: In hierdie proefskrif is 'n aantal mono- en di-gesubstitueerde asiel(ariel) tioureums ondersoek vir moontlike gebruik as ionofore (spesifieke draers) vir die transportasie en ekstraksie van Ag(l) vanuit 'n mengsel van Co(ll), Ni(II), Cu(II), Zn(II), Cd(II), Ag(l) en Pb(lI) ione. 'n Drie-fase selsisteem is gebruik vir die transportasie eksperimente, twee waterige fases (bron- en ontvang-fase) wat geskei is met die chloroform membraan fase wat die ligande bevat. Kompeterende metaalioon transportasie eksperimente is uitgevoer met behulp van hierdie vloeistof membraan stelsel. Die twee waterige fases is deur middel van Atoomabsorpsie Spektroskopie (AAS) ge-analiseer en resultate is bevestig met gebruik van Induktief-gekoppelde Plasma-Optiese Emissie Spektroskopie (IGP-OES). Die resultate het getoon dat elkeen van die N,N-dialkiel-gesubstitueerde-N'-asiel(ariel) (HL) tioureums, met uitsondering van N,N-di(2-hidroksie-etiel)-N'-benzieltioureum(HL 3) en Npiperidiel- N'-4-nitrobenzieltioureum(HL9 ), doeltreffend en selektief was vir Ag(l) transportasie. HL9 was selektief vir Ag(I), maar die transportasie waarde was nie hoog nie, dws. dit was nie doeltreffend nie. HL3 was selektief vir Cu(II). Met gebruik van ons eksperimentele kondisies is 13% Cu(lI) getransporteer deur HL 3. Van die N,N-dialkiel-N'- ariel tioureums, is maksimum transportasie van Ag(l) verkry met gebruik van N,N-dietiel- N'-4-chlorobenzieltioureum (HL5) en N,N-di-n-butiel-N'-benzieltioureum (HL1). Met gebruik van ons eksperimentele kondisies was die persentasie transportasie van Ag(l) deur HL5 en HL 1 48% en 42% onderskeidelik. Die selektiwiteit en doeltreffendheid van 3,3,3' ,3'-tetra-etiel-1 ,t-isoftaltelblstioureumtl+L 12) en N,N-di-etiel-N'-kamfonieltioureum (HL13) vir Ag(l) transportasie is ook onderneem. Ons was besonder ge-interesseerd om die Ag(l) transportasie en ekstraksie van hierdie ligande te vergelyk met dié van die HL en H2L tipe ligande. Die eksperimentele resultate het getoon dat van al die ligande wat bestudeer is, HL 13 die doeltreffendste en mees selektiewe ionofoor was. Van besondere, belang was dat, afhangend van die ligand konsentrasie wat gebruik is, HL13 71-81% Ag(l) getransporteer het. Kompeterende twee-fase metaalioon vloeistof-vloeistof ekstraksie eksperimente is ook uitgevoer onder toestande soortgelyk aan dié van die transportasie eksperimente. Die resultate toon dat met varierende ligand konsentrasie, tot soveel as 100% Ag(l) selektief en doeltreffend geëkstrakeer word vanuit 'n mengsel van die sewe metaal ione. N,N-di-n-butiel-N'-benzieltioureum (HL1 ) ligande en die kompleks daarvan met Ag(l) is ook gesintetiseer. Enkel-kristalle van die kompleks is verkry en X-straal kristallografiese analiese is onderneem. Die kristalstruktuur toon hoedat Ag(l) gebind is aan die gedeprotoneerde ligand deur die S en Q atome en toon ook interessante [Ag(L-S,Q)]4 groepe in die vaste toestand. Hierdie struktuur is monoklinies en kristaliseer in die ruimtegroep P21!c met a = 17.805(4) Á, b = 21.759(4)Á, c = 36.438(7)Á, P = 96.34(3t, z = 8 en 'n finale R-faktor van 5.4%.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

M.Sc. / This dissertation deals with the syntheses of tridentate (O^N^N) coordination ligands [{2,4-di-tert-butyl-6-[(2-(3,5-RR-pyrazol-1-yl-ethylimino)-methyl] phenol}, R = H (L1), Me(L2), Ph(L3), t-Bu(L4)], which was reacted initially with MX2 (M = Fe, Co, Ni; X = Cl, Br). The ligands L1-L4 were also modified by functionalizing the phenol group in this ligand group to an ethoxy in L5 and L6 (L5 = [(3,5-di-tert-butyl-2-ethoxy-benzylidene)-[2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-amine, L6 = [(3,5-di-tert-butyl-2-ethoxy-benzylidene)-[2-(3,5-di-tert-butyl-pyrazol-1-yl)-ethyl]-amine)], or into a phenoxy in L7 (L7 = (3,5-di-tert-butyl-2-phenoxy-benzylidene-(2-pyrazol-1-yl-ethyl)-amine)). Another ligand L8 (L8 = [4-(4-tert-butyl-benzylidene)-[2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-amine], which was devoid of the phenoxy group was also synthesized. These modified ligands were also reacted with MX2 or PdCl(COD)Me to form bidentate (N^N) chelating complexes. Further modification of the ligand L1-L4, to replace the phenoxy pyrazolylimine unit with a source of oxygen donor other than a phenoxy led to the use of already known ligands L9, L10 (L9 = 2-(3,5-dimethyl-pyrazol-1-yl)-ethanol, L10 = 2-(3,5-di-tert-butyl-pyrazol-1yl)-ethanol and L11, where in L11, the alcohol moiety is replaced by an electron withdrawing chloro group, L11 = 1-(2-chloroethyl)-3,5-di-methyl-pyrazole). These ligands were also reacted with MX2 (M = Fe, Co, Ni, Pd; X = Cl, Br) to form complexes. The synthesized complexes were characterized by a combination of IR and NMR spectroscopy, mass spectrometry, microanalysis and in selected cases single crystal X-ray crystallography.