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Humphrey, Paul Andrew. "A study of transition metal complexes /." Title page, contents and summary only, 1990. http://web4.library.adelaide.edu.au/theses/09PH/09phh9262.pdf.
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Marsh, Patrica Ann. "Metal complexes as precursors for film deposition processes." Thesis, Open University, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.262973.
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Li, Chi-kwan. "Gold(I) and Gold(II) phosphine complexes exhibiting weak AuI ... AuI interactions and unsupported AuII-AuII bonds : syntheses, spectroscopy, host-guest chemistry and reactivity studies /." Hong Kong : University of Hong Kong, 2002. http://sunzi.lib.hku.hk/hkuto/record.jsp?B25155295.
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Calatayud, Sanz Maria Pilar. "Self-assembled monolayers of metal complexes attached to gold electrodes." Thesis, University of Edinburgh, 2009. http://hdl.handle.net/1842/10851.
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In this thesis, ten different ligands were designed and synthesized in such a way as to provide metal containing SAMs. The metal binding sites of these ligands are derivatives of the tripodal ligand tris(2-pyridylmethyl)amine (TPA) and the tridentate amine bis(2-pyridylmethyl)amine (BPA), which have good molecular recognition properties in solution. As interface separating the electrode from the metal binding site and gold anchor group we have chosen a thiophenyl, thioethyl and thioctic acid groups. Electrochemical studies with [Fe(CN)6]3-/4- as redox probe in solution were carried out on SAMs of the TPA thioctic acid derivative L4 and its complexes Cu-L4, Zn-L4 and Fe-L4. Monolayers containing redox active Cu(II/I) ions accelerated the electron-transfer reaction (kapp = 2.78 x 10-2 cm/s) more than those containing Zn(II) (kapp = 1.51 x 10-4 cm/s) and Fe(II) (kapp = 1.40 x 10-3 cm/s) ions. This is consistent with a mechanism for electron-transfer in which the Cu ions exit in different coordination environments and with different redox potentials, and are rapidly undergoing interconversion. The ability of this system to facilitate the electron-transfer process to the redox probe was used to develop a new cyanide sensor. Addition of cyanide ions increases the blocking behaviour of the SAM, suggesting the elimination of Cu from the SAM to form [Cu(CN)n](n-1)- complexes. The cyanide detection limit was found to be 1 nM. Electrodes modified with the binucleating ligand 2,6-bis[bis(2-pyridylmethyl)amino-methyl]phenol thioctic acid derivative (bearing two BPA arms) L7 were also investigated. Metal containing SAMs can influence the electron-transfer process through the SAM to a solution containing a redox probe. This property can be used to develop new anion sensors in aqueous system.
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Choi, Wing-kin Sam. "Synthesis, photophysics and photochemistry of mono- and polynuclear complexes of gold /." Hong Kong : University of Hong Kong, 1995. http://sunzi.lib.hku.hk/hkuto/record.jsp?B17591168.
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陳展榮 and Chin-wing Chan. "Transition metal complexes of quaterpyridines and photochemical studies of cyclometallated gold(III) and platinum(II) complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1993. http://hub.hku.hk/bib/B31233454.
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Chan, Chin-wing. "Transition metal complexes of quaterpyridines and photochemical studies of cyclometallated gold(III) and platinum(II) complexes /." [Hong Kong : University of Hong Kong], 1993. http://sunzi.lib.hku.hk/hkuto/record.jsp?B13671753.
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Li, Chi-kwan, and 李志君. "Gold(I) and Gold(II) phosphine complexes exhibiting weak AuI... AuI interactions and unsupported AuII-AuII bonds: syntheses, spectroscopy, host-guest chemistry and reactivity studies." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2002. http://hub.hku.hk/bib/B31243332.
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Veenboer, Richard M. P. "Synthesis, study and application of NHC-gold(I) complexes." Thesis, University of St Andrews, 2017. http://hdl.handle.net/10023/12169.
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The development of procedures for the synthesis of valuable organic molecules constitutes an important part of chemistry. The goal of improving the efficiency of existing methodologies can be fulfilled by use of metal catalysts. Recent developments in the field of homogeneous gold catalysis have contributed to these efforts and continued investigations assure future innovations. Chapter 1 summarises the properties of gold and ligand-supported gold(I) complexes and demonstrates how a detailed understanding of its reactivity and possible bonding interactions with various substrates facilitates the development of well-defined catalytic systems. Particular attention is given to N-heterocyclic carbenes, highly tunable ligands that stabilise a wide range of different transition metal complexes. Three chapters describe syntheses and studies of known and new complexes. Chapter 2 discusses expedient syntheses of key NHC-gold(I) complexes and catalysts. Chapter 3 constitutes studies to the behaviour of the commonly used tetrafluoroborate counterion in a particular IPrCl -gold(I) complex. Chapter 4 de- scribes the synthesis of a range of IPr-gold(I) carbanion complexes from the widely studied IPr-gold(I) hydroxide synthon, the study of their properties and exploration of their reactivity. Catalytic applications in transformations of alkynes and alcohols are described in the last three chapters. Chapter 5 details the development of efficient NHC-gold(I)-catalysed procedures for the synthesis of vinyl ethers through addition reactions of aliphatic and benzylic alcohols to alkynes. Benzylic alcohols were found to undergo gold-catalysed dehydration under specific conditions and Chapter 6 discloses the NHC-gold(I)-catalysed dehydrative formation of ethers from phenols and benzylic alcohols. Appendix A describes preliminary explorations to the complimentary use of Brønsted acidic compounds as catalysts for the formation of products with new C – C bonds from benzylic alcohols and phenols.
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蔡永健 and Wing-kin Sam Choi. "Synthesis, photophysics and photochemistry of mono- and polynuclear complexes of gold." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1995. http://hub.hku.hk/bib/B31234781.
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Coventry, David N. "Tertiary-phosphine gold(I) and copper(I) complexes : precursors for metal deposition." Thesis, University of Edinburgh, 2002. http://hdl.handle.net/1842/12017.
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Tertiary-phosphine stabilised gold and copper complexes have been prepared with the intention to deposit elemental metal from solution. These complexes were intended to be delivered as a component of an ink on to a suitable substrate by an ink-jet printing process. Testing the compatibility of these complexes with ink-jet technology has been undertaken by Avecia and Seiko-Epson (this project's industrial sponsors). Four methyl(tertiary-phosphine)gold(I) complexes with a general molecular formula, [R3PAuCH3] (R = Ph, Ph-p-F, Ph-p-OMe and Me) were prepared by reacting (tertiary-phosphine)gold(I) chloride with methyllithium. Toluene-d8 and decalin solutions of these complexes were heated to 100°C and the rate of decomposition of each complex to gold(O), tertiary-phosphine and ethane was measured spectroscopically by NMR and GC respectively. Relatively the gold(I) complexes were found to decompose in the following order: Ph-p-F > Ph > Me >> Ph-p-OMe A series of tertiary-phosphine stabilised copper(I) aryloxide complexes, with the general molecular formula [{(RO)Cu(PR'3)m}n], were synthesised with the intent to duplicate the results obtained for the gold(I) complexes with a copper system. All the copper(I) complexes prepared were found to be too thermally stable to be suitable for the aim of the project. During the course of this project it was noted that the steric and electronic factors involved in producing the thermodynamic product from the reaction mixture were of major importance in the design of such complexes. Increase in overall steric bulk was, as expected, found to lead to copper(I) ions with lower coordination numbers while an increase in the electron affinity of the ligands was found to produce complexes with copper ions with higher coordination numbers.
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Nyamwihura, Rogers. "Synthesis of Gold Complexes From Diphosphine Ligands and Screening Reactions of Heterocyclic Acetylacetonato (ACAC) Ligands with Transitional Metal Complexes." Thesis, University of North Texas, 2015. https://digital.library.unt.edu/ark:/67531/metadc804890/.
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Syntheses of diphosphine gold (I) complexes from gold THT and two ligands, 4, 5-bis (diphenylphosphino)-4-cyclopenten-1, 3-dione (BPCD) and 2,3-bis(diphenylphosphino)-N-phenylmaleimide (BPPM), were done separately. The reactions happened under ice conditions followed by room temperature conditions and produced two diphosphine gold (I) complexes in moderated yield. Spectroscopic results including nuclear magnetic resonance (NMR) and X-ray crystallography were used to study and determine the structures of the products formed. Moreover, X-rays of all newly synthesized diphosphine gold (I) complexes were compared with the known X-ray structures of other phosphine and diphosphine gold (I) complexes. There were direct resemblances in terms of bond length and angle between these new diphosphine gold (I) complex structures and those already published. For instance, the bond lengths and angles from the newly prepared diphosphine gold (I) complexes were similar to those already published. Where there were some deviations in bond angles and length between the newly synthesized structures and those already published, appropriate explanation was given to explain the deviation. Heterocyclic ligands bearing acetylacetonate (ACAC) side arm(s) were prepared from ethyl malonyl chloride and the heterocyclic compounds 8-hydroxylquinoline, Syn-2-peridoxyaldoxime, quinoxalinol and 2, 6-dipyridinylmethanol. The products (heterocyclic ACAC ligands) from these reactions were screened with transition metal carbonyl compounds in thermolytic reactions. The complexes formed were studied and investigated using NMR and X-ray crystallography. Furthermore, the X-ray structures of the heterocyclic ACAC ligand or ligand A and that of rhenium complex 1 were compared with similar published X-ray structures. The comparison showed there were some similarities in terms of bond length and bond angles.
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Yan, Kun. "Proteomic and biochemical studies of cytotoxic gold(I), silver(I) and rhodium(II) complexes." Click to view the E-thesis via HKUTO, 2007. http://sunzi.lib.hku.hk/hkuto/record/B3963436X.
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Rogers, Nicola Jane. "The development of gold nanoparticles labelled with transition metal complexes for imaging applications." Thesis, University of Birmingham, 2014. http://etheses.bham.ac.uk//id/eprint/5058/.
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13 nm and 100 nm citrate-stabilised gold nanoparticles are used as inert scaffolds for the assembly of multiple transition metal lumiphores, and thiol-appended ruthenium(II) and iridium(III) polypyridyl complexes have been synthesised for surface-attachment. The direct attachment of cationic lumiphores to citrate-stabilised gold colloids with negative zeta potentials, affords nanoparticle aggregation, due to loss of electrostatic stabilisation. In order to circumvent this problem, a surfactant pre-coating step has been implemented, and the following commercial surfactants have been evaluated: Triton™ X-100, TWEEN® 20, and Zonyl® 7950. Gold nanoparticles coated with Zonyl® 7950 fluorosurfactant can be functionalised with cationic lumiphores and colloidal stability is maintained even at high nanoparticle concentrations, i.e. 9 nM. The fluorosurfactant not only ensures colloidal stability, but also enhances the emission of the ruthenium(II) and iridium(III) complexes investigated. Importantly, the complexes attached on the resultant luminescent nanoprobes do not exhibit luminescence quenching from the gold nanoparticles. Imaging applications of the resultant luminescent nanoparticles have been demonstrated in in vitro cellular uptake studies and in blood flow particle tracking within the microvasculature. Furthermore, gold nanoparticles have been co-coated with lumiphores and both functional peptides, for targeted delivery in cells, and gadolinium(III) complexes, in order to realise imaging probes for both luminescence and MRI detection.
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Santos, Vanessa Nascimento dos. "Gold electrode modified with inorganic complexes applied as electrochemical sensors for nitric oxide." Universidade Federal do CearÃ, 2012. http://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=7264.
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Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgicoThe aim of this work is to study the surface modification of gold electrode with the trans-[Ru(NH3)4(tina)(SO4)]+ (Au/trans-[Ru(NH3)4(tina)(SO4)]+) and trans-[Fe(cyclam)(NCS)2]+ (Au/trans-[Fe(cyclam)(NCS)2]+) complexes ion, emplyoing the electrodeposition and self-assembled monolayer techniques, respectively; and evaluate the potentiality of these modified electrodes as electrochemical sensors for detection and quantification of NO. Cyclic voltammetry and electrochemical quartz crystal microbalance results suggest that the deposition of trans-[Ru(NH3)4(tina)(SO4)]+ complex ion on the gold surface. Cyclic voltammetry and surface enhanced raman spectroscopy results confirm the modification of gold electrode surface by the trans-[Fe(cyclam)(NCS)2]+ complex ion. Peak current (Ip) observed in cyclic voltammograms for the oxidation of NO on the modified electrodes were higher than that observed for the unmodified gold electrode, and the modified electrode Au/trans-[Fe(cyclam)(NCS)2]+ showed the highest Ip for the oxidation of NO. The values of detection limit and quantification limit obtained for the electrode Au/trans-[Ru(NH3)4(tina)(SO4)]+ were 7.73 x 10-8 mol L-1 and 2.58 x 10-7 mol L-1, and for the electrode Au/trans-[Fe(cyclam)(NCS)2]+ were 5.15 x 10-8 mol L-1 and 1.72 x 10-7 mol L-1, respectively, being this values smaller by an order of magnitude as the same obtained for the unmodified gold electrode. Computational simulations suggest that the increase in Ip oxidation of NO on the electrode Au/trans-[Fe(cyclam)(NCS)2]+ is due to the interaction energy between molecules of NO and the complex trans-[Fe(cyclam)(NCS)2]+, adsorbed on the gold surface, to be stronger than the energy of interaction of NO with the gold surface. The dopamine and serotonin molecules and the nitrite ion interfere in electrochemical detection of NO and dopamine and serotonin showed greater interference in the detection of NO in relation to the nitrite ion. The electrode Au/trans-[Fe(cyclam)(NCS)2]+ showed the greatest stability when compared to the electrode Au/trans-[Ru(NH3)4(tina)(SO4)]+. The results obtained in this work showed the potentiality of modified electrodes as sensors for deteccion and quantification of NO, among which stands out the electrode Au/trans-[Fe(cyclam)(NCS)2]+ due to the further intensification of the signal current for the oxidation of NO and provided greater stability.
O objetivo deste trabalho à estudar a modificaÃÃo da superfÃcie do eletrodo de ouro com os Ãons complexos trans-[Ru(NH3)4(tina)(SO4)]+ (Au/trans-[Ru(NH3)4(tina)(SO4)]+) e trans-[Fe(cyclam)(NCS)2]+ (Au/trans-[Fe(cyclam)(NCS)2]+), empregando as tÃcnicas de eletrodeposiÃÃo e formaÃÃo de camadas auto-organizadas, respectivamente; e avaliar a potencialidade destes eletrodos modificados como sensores eletroquÃmicos para detecÃÃo e quantificaÃÃo de NO. Os resultados de voltametria cÃclica e de microbalanÃa eletroquÃmica a cristal de quartzo sugerem a deposiÃÃo do Ãon complexo trans-[Ru(NH3)4(tina)(SO4)]+ sobre a superfÃcie de ouro. Os resultados de voltametria cÃclica e de espalhamento raman amplificado por superfÃcie comprovam a modificaÃÃo da superfÃcie do eletrodo de ouro pelo Ãon complexo trans-[Fe(cyclam)(NCS)2]+. As correntes de pico (Ip) observadas nos voltamogramas cÃclicos para a oxidaÃÃo do NO sobre os eletrodos modificados foram maiores que as observadas para o eletrodo de ouro sem modificaÃÃo, sendo que o eletrodo modificado Au/trans-[Fe(cyclam)(NCS)2]+ apresentou a maior Ip para a oxidaÃÃo de NO. Os valores de limite de detecÃÃo e de quantificaÃÃo obtidos para o eletrodo Au/trans-[Ru(NH3)4(tina)(SO4)]+ foram de 7,73 x 10-8 mol L-1 e 2,58 x 10-7 mol L-1, e para o eletrodo Au/trans-[Fe(cyclam)(NCS)2]+ foram de 5,15 x 10-8 mol L-1 e 1,72 x 10-7 mol L-1, respectivamente, sendo estes valores menores em uma ordem de grandeza que os mesmos obtidos para o eletrodo de ouro nÃo modificado. As simulaÃÃes computacionais sugerem que o aumento de Ip da oxidaÃÃo de NO sob o eletrodo Au/trans-[Fe(cyclam)(NCS)2]+ à devido à energia de interaÃÃo entre as molÃculas de NO e o complexo trans-[Fe(cyclam)(NCS)2]+, adsorvido na superfÃcie de ouro, ser mais forte que a energia de interaÃÃo do NO com a superfÃcie de ouro. As molÃculas dopamina e serotonina e o Ãon nitrito interferem na detecÃÃo eletroquÃmica de NO e a dopamina e a serotonina apresentaram maior interferÃncia na detecÃÃo de NO em relaÃÃo ao Ãon nitrito. O eletrodo Au/trans-[Fe(cyclam)(NCS)2]+ apresentou maior estabilidade quando comparado ao eletrodo Au/trans-[Ru(NH3)4(tina)(SO4)]+. Os resultados obtidos neste trabalho demonstram a potencialidade dos eletrodos modificados como sensores para detecÃÃo e quantificaÃÃo de NO, dentre os quais se destaca o eletrodo Au/trans-[Fe(cyclam)(NCS)2]+, devido à maior intensificaÃÃo no sinal de corrente para a oxidaÃÃo de NO e a maior estabilidade apresentada.
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Cheung, Kai-leung. "Syntheses and luminescence studies of di- and polynuclear gold(1) and copper(1) complexes, design strategies towards metalloreceptors and mixed-metal complexes /." Hong Kong : University of Hong Kong, 2001. http://sunzi.lib.hku.hk/hkuto/record.jsp?B23736136.
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張碧玉 and Pik-yuk Christine Cheung. "Crystal structure analysis of imido, nitrido and oxo complexes of rhenium (V), osmium (VI) and ruthenium (III) and some complexes oftrinuclear gold (I)." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1991. http://hub.hku.hk/bib/B31210211.
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Cheung, Pik-yuk Christine. "Crystal structure analysis of imido, nitrido and oxo complexes of rhenium (V), osmium (VI) and ruthenium (III) and some complexes of trinuclear gold (I) /." [Hong Kong : University of Hong Kong], 1991. http://sunzi.lib.hku.hk/hkuto/record.jsp?B13138327.
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Esterhuysen, Matthias Wilhelm. "Reactions of gold(I) electrophiles with nucleophiles derived from group 6 Fischer-type carbene complexes." Thesis, Stellenbosch : University of Stellenbosch, 2003. http://hdl.handle.net/10019.1/16046.
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Dissertation (PhD)--University of Stellenbosch, 2003.ENGLISH ABSTRACT: This study comprises the preparation and characterisation of various novel organometallic species of gold(I) by employing a range of anionic group 6 metal Fischer-type carbene complexes and group 6 metal-acyl complexes as synthons of the organic moieties introduced to the gold(I) electrophiles. The main objectives of this work are to develop the use of Fischer-type carbene complexes as synthons in the preparation of novel organometallic species along unusual reaction pathways and, in doing so, to expand the organometallic chemistry of gold(I), especially Au-C bond formation reactions. By reacting various β-CH acidic Fischer-type alkoxy/dialkylamino/ alkthio(methyl)carbene complexes, first with a base, and then with a gold(I) electrophile (Ph3PAu+), easy access to vinyl ether/dialkylamine/thioether complexes of gold(I) coordinated to M(CO)5 (M = Cr, Mo, W) fragments, is obtained. When methyl alkoxy- or dialkylaminocarbene complexes are employed, coordination of the novel alkoxyvinyl-gold(I)PPh3 and dialkylaminovinyl-gold(I)PPh3 species to the M(CO)5 fragments occurs in an asymmetrical fashion through the vinyl functionalities of the novel gold(I) species. This usually unstable coordination mode for vinyl ethers is stabilised by delocalisation of partial positive charges from the α-gold vinyl carbon atoms to either the gold(I)PPh3 fragment [for η2-{alkoxyvinyl-gold(I)PPh3}M(CO)5 complexes] or the nitogen atoms of the vinyl amine group [for η2-{dialkylaminovinylgold( I)PPh3}M(CO)5 complexes]. In the latter complexes this delocalisation occurs to such an extent that these complexes are best described as zwitterions. The corresponding negative charges in the bimetallic complexes reside on the M(CO)5 fragments. As a representative example, uncoordinated ethoxyvinyl-gold(I)PPh3 was isolated in high yield via a ligand replacement reaction with PPh3. When Fischer-type alkthio(methyl)carbene complexes are employed in this conversion, novel sulphur coordinated {alkthiovinyl-gold(I)PPh3}Cr(CO)5 complexes are formed.The reaction mechanism involved in these conversions is believed to be the gold(I) analogue of the hydrolysis of Fischer-type carbene complexes. In this mechanism the bimetallic η2-vinyl ether coordinated {alkoxyvinyl-gold(I)PPh3}M(CO)5 complexes represent stabilised gold(I) analogues of postulated transition states in the hydrolytic decomposition of Fischer-type alkoxycarbene complexes. The term aurolysis is conceived to describe the conversion when Ph3PAu+ is employed as electrophile instead of H+. The formation of the bimetallic η2-vinyl ether coordinated complexes in the current conversion, furthermore, strongly supports the existence of similar transition states in the hydrolytic decomposition of Fischer-type alkoxycarbene complexes. This mechanism is also accepted for the formation of analogous η2-{dialkylaminovinyl-gold(I)PPh3}M(CO)5 and {alkthiovinyl-gold(I)PPh3}-S Cr(CO)5 complexes when β-CH deprotonated Fischer-type dialkylamino- and alkthiocarbene complexes are employed in this reaction. The reaction of anionic group 6 metal-acyl complexes and their nitrogen analogues, N-deprotonated Fischer-type aminocarbene complexes, leads to the formation of acylgold(I) and novel imidoylgold(I) complexes coordinated to M(CO)5 (M = Cr, W) fragments. In the previous complexes poor stabilisation of the M(CO)5 fragments allows halide anions to readily form ionic adducts with these groups. This characteristic of these products provides a useful reaction pathway to the first example of a free acylgold(I) complex, benzoyl-AuPPh3. Coordination of the imine nitrogen atom to the M(CO)5 fragments in the analogous bimetallic imidoylgold(I)-M(CO)5 complexes is much stronger. These complexes are remarkably stable and could even be effectively isolated by means of low temperature silica gel chromatography. As a preliminary reaction mechanism for this conversion we propose a mechanism that is closely related to the aurolysis mechanism described above. The only difference is that, instead of formal reductive elimination of vinyl ethers/amine/thioether complexes of gold(I) from the M(CO)5 fragments, acyl and imidoyl complexes of gold(I) are produced in this step. Furthermore, the (Z)- stereoisomers of the bimetallic imidoylgold(I)-M(CO)5 complexes generated in this conversion are exclusively obtained.A second N-deprotonation-auration reaction sequence performed on suitable examples of the bimetallic imidoylgold(I)-M(CO)5 complexes yields, as the only isolable product, a novel triangular Au2Cr cluster complex, cis-{η2-(Ph3PAu)2} PPh3Cr(CO)4. This complex is the isolobal equivalent for the unstable molecular hydrogen complex, (η2-H2)PPh3Cr(CO)4, and exhibits the shortest known Au-Au separation between two gold atoms in cluster complexes of the type Au2M. Finally, two novel and vastly different molecular structures of closely related anionic benzoylpentacarbonyl tungstates, one with Li+ as counterion and another in which exactly half the Li+-cations have been replaced by protons, highlight the importance of hydrogen bonding and ion-dipole interactions in determining the solid state structure of such complexes.
AFRIKAANSE OPSOMMING: Hierdie studie behels die bereiding en karakterisering van verskeie nuwe organometaalkomplekse van goud(I). Hierdie komplekse is berei deur gebruik te maak van n wye reeks anioniese groep 6 metaal Fischer-tipe karbeenkomplekse asook anioniese groep 6 metaal asielkomplekse as sintetiese ekwivalente vir die organiese fragmente wat gedurende die sintese aan die goud atoom gebind word. Die hoofdoel van hierdie studie is om die gebruik van Fischer-tipe karbeenkomplekse as sintetiese voorgangers in die bereiding van nuwe organometaalverbindings te ontwikkel en om sodoende ook die organometaalchemie van goud verder uit te bou. Veral die ontwikkeling van nuwe sintetiese metodologieë vir die bereiding van Au-C bindings is hier van belang. Verskeie Fischer-tipe alkoksie-/dialkielamino-/alktio-(metiel)karbeenkomplekse met suuragtige waterstofatome geleë op die β-metallo-koolstofatoom is eers onomkeerbaar gedeprotoneer. Byvoeging van die goud(I) elektrofiel, Ph3PAu+, lei - volgens n ongewone reaksiemeganisme - tot die vorming van onderskeie vinieleter-, dialkielvinielamien- en vinieltioeterkomplekse van goud(I). Hierdie komplekse is verder ook op verskillende wyses aan M(CO)5 fragmente (M = Cr, Mo, W) gekoördineer. Die vinieleter- en vinielamienkomplekse van goud(I), wat vorm wanneer alkoksie- en dialkielaminokarbeenkomplekse onderskeidelik in hierdie sintese aangewend word, koördineer onsimmetries deur hulle viniel dubbelbindings aan die vrygestelde M(CO)5-groepe. Hierdie normaalweg onstabiele vorm van vinieleterkoördinasie, word gestabiliseer deur delokalisering van positiewe lading vanaf die α-goud viniel koolstofatoom na die AuPPh3-fragment [vir die η2-{alkoksievinielgoud( I)PPh3}M(CO)5 komplekse] óf na die stikstofatoom van die dialkielvinielamien groep [vir die η2-{dialkielaminoviniel-goud(I)PPh3}M(CO)5 komplekse]. Laasgenoemde komplekse kan as zwitterione beskryf word. Die onderskeie negatiewe ladings in hierdie komplekse bevind hulle hoofsaaklik op die M(CO)5 groepe. Sterk koördinerende ligande (bv. PPh3) verplaas die onsimmetriese viniel eter vanaf die M(CO)5-fragment. Só kon, as n voorbeeld, die vrye etoksievinielgoud( I)PPh3-kompleks met n hoë opbrengs berei word. Wanneer β-gedeprotoneerdeFischer-tipe tiokarbeenkomplekse met Ph3PAu+ reageer, vorm swawel gekoördineerde {tioviniel-goud(I)PPh3}Cr(CO)5 bimetalliese komplekse in stede van die π-komplekse. Dit word voorgestel dat in die bogenoemde reaksies die goud(I)elektrofiel dieselfde rol vervul as die proton gedurende die hidrolise van Fischer-tipe alkoksiekarbeenkomplekse. Die bimetalliese, η2-vinieleter-gekoördineerde {alkoksieviniel-goud(I)PPh3}M(CO)5-komplekse hier berei verteenwoordig dus stabiele goud(I) analoë van voorgestelde tusseprodukte in so ’n meganisme. Die term aurolise word voorgestel om die geval waar Ph3PAu+ in stede van H+ as elektrofiel aangewend word te beskryf. Die vorming van bimetalliese, η2-vinieletergeko ördineerde komplekse in die huidige reaksie ondersteun die moontlike vorming van die voorgestelde tussenprodukte tydens die hidrolise van Fischer-tipe alkoksie(metiel)karbeenkomplekse. ’n Soortgelyke meganisme kan ook gebruik word om die vorming van die η2-{dialkiellamienviniel-goud(I)PPh3}M(CO)5- en {alktioviniel-goud(I)PPh3}-S Cr(CO)5-komplekse vanuit β-CH gedeprotoneerde Fischer-tipe dialkielamino- en tiokarbeenkomplekse en Ph3PAuCl te interpreteer. Die reaksie van anioniese groep 6 oorgangsmetaal metaal-asielkomplekse en hulle stikstofanaloë, N-gedeprotoneerde Fischer-tipe aminokarbeenkomplekse, lewer onderskeidelik asiel- en imidoielkomplekse van goud(I) wat aan M(CO)5 fragmente (M = Cr, W) koördineer. Die goud(I)asiel-M(CO)5 koördinasie deur die asielsuurstofatoom is baie swak en die M(CO)5-eenheid in hierdie komplekse word maklik deur haliedanione en sekere oplosmiddel molekules verplaas. Die haliedanione vorm anioniese addukte met the M(CO)5 fragmente. Hierdie eienskap van die bimetalliese komplekse verskaf sodoende n gerieflike sintetiese roete na die eerste voorbeeld van n vrye asielgoud(I)-kompleks, bensoiel-AuPPh3. Koördinasie van die imienstikstofatoom aan M(CO)5-groepe in die bg. imidoielkomplekse is egter veel sterker. Die bimetalliese {imidoielgoud(I)}M(CO)5-komplekse is verbasend stabiel en kan selfs effektief deur middel van lae temperatuur SiO2-kolomkromatografie geïsoleer word. n Soortgelyke reaksie meganisme as wat voorgestel word vir die aurolise van Fischer-tipe karbeenkomplekse word voorgestel vir hierdie reaksie. Die enigste verskil is dat die formele reduktiewe eliminasie van n viniel-eter, -amien of -tioeter vervang word met die vorming van asiel- of imidoielkomplekse van goud(I). Verder word die (Z)-isomere van die bimetalliese {imidoielgoud(I)}M(CO)5-komplekse uitsluitlik in hierdie reaksie verkry. Wanneer geskikte voorbeelde van bimetalliese {imidoielgoud(I)}M(CO)5-komplekse n tweede keer gedeprotoneer word en gereageer word met Ph3PAuCl, is die enigste isoleerbare produk van die reaksie n driehoekige Au2Cr troskompleks, nl. cis-{η2- (Ph3PAu)2}PPh3Cr(CO)4. Hierdie verbinding dien as n isolobale model vir die onstabiele molekulêre waterstof kompleks , (η2-H2)PPh3Cr(CO)4, en besit verder die kortste Au-Au afstand tussen twee goud atome in driehoekige troskomplekse wat nog tot dusvêr gerapporteer is. Laastens is die kristalstrukture van twee nou verwante anioniese {bensoiel}W(CO)5- komplekse bepaal. Die enigste verskil tussen die hierdie twee verbindings is dat die een slegs Li+ as teenioon bevat terwyl presies die helfte van die Li+-teenione in die tweede struktuur deur protone verplaas is. Hierdie klein verskil in samestelling veroorsaak egter drastiese verskille in die kristalstrukture van hierdie verbindings. Die belangrikheid van waterstof bindings en ioon-dipool interaksies in die bepaling van die vastetoestandstrukture van sulke verbindings word hierdeur beklemtoon.
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Yan, Kun, and 嚴琨. "Proteomic and biochemical studies of cytotoxic gold(I), silver(I) and rhodium(II) complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2007. http://hub.hku.hk/bib/B3963436X.
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張啓亮 and Kai-leung Cheung. "Syntheses and luminescence studies of di- and polynuclear gold(1) and copper(1) complexes, design strategies towards metalloreceptors andmixed-metal complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2001. http://hub.hku.hk/bib/B31242996.
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Chan, Chi-keung. "Structure, photophysical and theoretical studies of polynuclear CU(I), AG(I) and AU(I) metal complexes /." Hong Kong : University of Hong Kong, 1997. http://sunzi.lib.hku.hk/hkuto/record.jsp?B18037422.
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Caporale, Angelamaria. "Synthesis of novel ligands for the stabilization of organometallic complexes having potential antitumor activity." Doctoral thesis, Universita degli studi di Salerno, 2016. http://hdl.handle.net/10556/2191.
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2014 - 2015The design of new metal complexes as anticancer agents has received considerable interest in recent years. Complexes of titanium (e.g.: titanocene dichloride), lanthanides complexes (e.g.: texaphyrrins lanthanide) and carbenic complexes of gold, silver and copper showed significant biological activity, and have progressed into clinical trials. Thus, the target of this PhD project are the synthesis of new ligands and metal complexes. Firstly 5 cyclopentadienyl pro-ligands were synthesised: 6-phenylfulvene, 6-(p-metoxyphenyl)-fulvene e 6- (3',4'-dymethoxyphenyl)fulvene, 6-(3',5')-dymethoxyphenyl)fulvene and 6-(2',4')- dymethoxyphenyl)fulvene. Then, the synthesis of 12 novel scandium, yttrium and neodymium complexes with these cyclopentadienyl ligands was carried out. The complexes were tested on DU146 (Prostatic carcinoma) and MDA.MB213 (Breast cancer) to verify inhibition of cell-proliferation, using MTT test with standard procedures. All the complex showed a strong concentration-dependent ability of inhibiting the growth tumor cell, referring to antiblastic activity. [edited by author]
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Cheng, Chung-chin. "Syntheses and photophysics of luminescent polynuclear coinage metal complexes with chalcogen and pnictogen containing bridging ligands /." Hong Kong : University of Hong Kong, 2001. http://sunzi.lib.hku.hk/hkuto/record.jsp?B22956372.
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Gasperini, Danila. "Design and study of novel gold complexes for efficient catalytic process towards the activation of alkynes." Thesis, University of St Andrews, 2018. http://hdl.handle.net/10023/14247.
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Gold has emerged as valuable tool for chemists. The physico-chemical properties of the metal centre make it exceptionally prone to activate multiple bonds, such as alkynes and alkenes. Thus, its utility in catalysis has been exploited together with the synthesis of suitable catalysts to allow new, efficient transformations, and the understanding of their intrinsic mechanisms. Reported in this thesis are efforts to this goal, such as the design and study of new Au(I) and Au(III) complexes towards functionalisation of alkynes. The development of new catalytic systems is tackled in Chapter 2. An efficient method for the intermolecular hydrocarboxylation of alkynes catalysed by dinuclear Au-NHC species to access diverse vinyl esters in excellent yield and stereoselectivity is described. The successful methodology is followed by the straightforward intramolecular hydrocarboxylation of alkynoic acids to allow the stereoselective and regioselective synthesis of γ-, δ- and ε-lactones in high yield. Initial mechanistic studies into the hydrocarboxylation of alkynes are shown in Chapter 3. The discovery and characterisation of novel dinuclear gold carboxylates species is described, and their role in the catalytic inter- and intramolecular process is investigated. Chapter 4 highlights the synthesis of novel Au complexes bearing chiral isothiourea ligands. Neutral and heteroleptic Au(I) and Au(III) species are obtained in excellent yield, and their solution and solid-state behaviour studied, together with their electronic and steric properties. Further testing towards activation and functionalisation of alkynes and propargylic derivatives are shown. Dual catalytic processes involving Au and isothiourea catalysts are presented in Chapter 5. Attempts towards Lewis acid/Lewis base activation of multiple bond derivatives and activated esters towards the formation of new C-C bonds is described. The synthesis of organogold compounds, bearing NHC ligands, is described in Chapter 6. Through deprotonation of C(sp3 )-H bonds, a series of stable gold(I) complexes was synthesised and found to be suitable synthons to different gold species. Finally, the redox chemistry of organogold species is explored.
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Crawford, Deborah Elizabeth. "Luminescent diphosphine gold complexes with potential as sensors : structures, optical properties and reactivity with metal ions." Thesis, Queen's University Belfast, 2015. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.680175.
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This project involves the study of new molecular sensors based on luminescent compounds that can change their emission properties in the presence of an analyte, in particular 'spectroscopically silent' metals, particularly those important in nature, such as Zn or Cu. Gold(l) complexes exhibiting Au--Au (aurophilic) interactions are often highly luminescent, and their emission can be related to the presence of such weak interactions. There is, however, a lack of understanding on how to control the extent of the interactions and the influence that these may have on the structures and optical behaviour of the compounds. The present work involves the systematic study of the influence that Au--Au and other weak interactions (Au--X, X = 0, S) have on the overall structures of digold(l) compounds as well as on their luminescence spectra, both in solid and solution states. These secondary interactions were investigated by varying both the heteroatom present in the bridging diphosphine ligand and the range of thiolate and alkyne co-ligands coordinated through the Au(l) atom. The potential of the compounds as optical sensors towards other metal ions has been investigated. Within this study, some very interesting X-ray crystal structures were obtained and described e.g. an unusual Au4Ag4 cluster.
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Chan, Chi-keung, and 陳志強. "Structure, photophysical and theoretical studies of polynuclear CU(I),AG(I) and AU(I) metal complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1997. http://hub.hku.hk/bib/B31235554.
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鄭重展 and Chung-chin Cheng. "Syntheses and photophysics of luminescent polynuclear coinage metal complexes with chalcogen and pnictogen: containing bridging ligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2001. http://hub.hku.hk/bib/B31241530.
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Levesque, Patrick Pierre. "Development of New Biarylphosphane Coinage Metal Complexes for the Regioselective Synthesis of Fused Carbocycles." Thèse, Université d'Ottawa / University of Ottawa, 2012. http://hdl.handle.net/10393/23367.
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In the last century, no less than five nobel prizes have been awarded for the construction of carbon-carbon bonds : The Grignard reaction (1912), the Diels-Alder reaction (1950), the Wittig reaction (1979), Olefin metathesis (2005) and palladium cross-coupling reactions (2011). The latter two are transition metal catalyzed transformations and their impact on the synthesis of pharmaceutically active compounds, bulk chemicals, fine chemicals, high tech materials as well as agricultural chemicals has been phenomenal. These reactions have changed the way the scientific community views the science of synthesis. Unlike palladium, gold has long been considered to be an expensive and inert metal and therefore, research on Au catalysis was scarse until the begining of the new millenium. Once the scientific community realized the treasure trove of reactivity that gold had to offer, the number of chemical transformations as well as total syntheses involving Au(I)/Au(III) catalysis has sky rocketed. A methodology initially developped by Toste and coworkers has shown that intramolecular addition of a silyl enol ether on alkynes proceeds via a 5-exo¬-dig¬ process. In the first part of this thesis, we will discuss how the ancilary ligand on Au(I) species can influence pathway selectivity for these cyclizations, therefore opening the door to selective 6-endo-dig cyclizations to generate fused carbocycles. With biological processes as well as other competing processes becoming ever more efficient, the future of chemical synthesis is threatened. If it is to survive, the focus of new chemical transformations will have to be on the cost and the greeness of the process. In the second part of this thesis, we will demonstrate how Ag(I) and Cu(I) complexes can offer even better 6-endo-dig¬ selectivity than analogous Au(I) complexes. Silver is about 56 times less expensive than gold, and copper is about 453 times less expensive than gold. Due to the greatly increased selectivity as well as the diminished cost of the catalysts, we have provided access to an attractive 6-endo-dig¬ cyclization process.
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Zhang, Chen. "Metal-NHC complexes for anti-cancer applications : gold(I) for antimitochondrial activity and iridium(III) for photodynamic therapy." Thesis, Toulouse 3, 2018. http://www.theses.fr/2018TOU30129/document.
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Dans ce travail de thèse, plusieurs groupes de nouveaux complexes d'or(I) à base de carbènes N-hétérocyclique (NHC)contenant des bras amino-aliphatiques et aromatiques avec un potentiel intéressant dans des applications biomédicales ont été synthétisés et entièrement caractérisés. En outre, une série de complexes d'iridium(III) contenant des ligands NHC avec des activités anticancéreuses prononcées pour une application en thérapie photodynamique, a étépréparée et entièrement caractérisée. Le premier groupe représente une famille de complexes cationiques or(I) bis(NHC) contenant des bras latéraux amino-aliphatiques. Ces complexes ont étésynthétisés et étudiés pour leurs activités antiprolifératives vis-à-vis de quatre lignées cellulaires cancéreuses humaines et de la lignée cellulaire non cancéreuse MDCK. Dans cette série, la lipophilie est directement liée àl'activitécytotoxique contre les cellules cancéreuses. La deuxième famille de composés concerne les complexes cationiques or(I) bis(NHC) contenant des bras latéraux amino-aromatiques. La cytotoxicitéin vitro de ces complexes et de leurs proligands sur les lignées cellulaires représentatives du cancer de la prostate PC-3 et de la vessie T24 a étéévaluée. Tous ces complexes présentent des valeurs de Log P (lipophilie) supérieures àcelles de la première série de complexes en accord avec leur cytotoxicité plus élevée, mais une lipophilie trop élevée peut également conduire àune sélectivitéplus faible. Afin de développer un candidat-médicament avec une activitéet une sélectivité optimisées, nous avons conçu et synthétisé la troisième famille de complexes cationiques or(I) bis(NHC). Les valeurs de log P de cette série se situent entre la première série et la deuxième série. Ces complexes moins lipophiles sont moins cytotoxiques envers les lignées cellulaires saines (NIH3T3) et montre des activités anticancéreuses un peu plus faibles sur les cellules PC-3 que la deuxième série, avec néanmoins des valeurs de GI50 dans la gamme du nanomolaire. Les études mécanistiques sur deux complexes d'or(I) ont été réalisées. Les mesures d'absorption cellulaire ont montré une accumulation cellulaire rapide et une bonne biodisponibilitédes complexes, en accord avec l'activitéantiproliférative de ces deux complexes. De plus, les deux complexes inhibent la thiorédoxine reductase (TrxR), une cible commune pour les complexes d'or(I). La mort cellulaire induite par ces deux complexes est dépendante des espèces réactives de l'oxygène. En plus des activités anticancéreuses, nous avons également testédes complexes d'or(I) mono-NHC pour une autre application biomédicale, la leishmaniose, maladie parsitaire. Ils ont été testés in vitro sur les formes promastigotes et amastigotes axéniques de L. infantum. De plus, leur cytotoxicitéa étéévaluée sur les macrophages murins J774A.1 afin de déterminer leur sélectivitéd'action. Un autre sujet de cette thèse concerne les complexes d'iridium(III)-NHC. Trois familles de complexes ont étépréparées et caractérisées. La cytotoxicitéin vitro de tous les complexes sur les cellules cancéreuses de la prostate PC-3 et de la vessie T24, et les cellules non cancéreuses NIH3T3 a étéévaluée. De plus, tous les complexes sont des agents théranostiques, et les expériences de microscopie confocale d'un complexe ont montréqu'il pouvait être rapidement et efficacement absorbédans les cellules PC-3 et se localiser spécifiquement dans les mitochondries. De manière intéressante, ces complexes peuvent agir comme des photosensibilisateurs efficaces. La cytotoxicitéde ces complexes a étéaugmentée substantiellement après une irradiation lumineuse de 365 nm, ce qui suggère le potentiel élevéde ces agents anticancéreux théranostiques ciblant les mitochondries pour la thérapie photodynamiqueIn this work of thesis, several groups of novel NHC-based gold(I) complexes containing aliphatic and aromatic amino-side arms with interesting potential in biomedical applications have been synthesized and fully characterized. Also, a series of iridium(III) complexes containing NHC ligands with pronounced PDT anticancer activities has been prepared and fully characterized. The first group represents a family of cationic bis(NHC)-gold(I) complexes containing aliphatic amino-side arms. These complexes have been synthesized and investigated for their antiproliferative activities towards four human cancer cell lines and the non-cancerous MDCK cell line. In this series, the lipophilicity correlates directly with the cytotoxic activity against cancer cells. The second family of compounds concerns cationic gold(I) bis(NHC) complexes containing aromatic amino-side arms. The in vitro cytotoxicity of these complexes and proligands on the representative PC-3 prostate and T24 bladder cancer cell lines has been evaluated. All these complexes show higher Log P values (lipophilicity) than the first series of complexes, and in line with this higher cytotoxicity, nevertheless too high lipophilicity can also lead to lower selectivity. In order to develop a drug candidate with optimized activity and selectivity, we designed and synthesized the third family of cationic gold(I) bis(NHC) complexes. The Log P values of this series were between the first series and the second series. The lower cytotoxicity towards non-cancerous NIH3T3 cells was found for this series of complexes whereas they also displayed less activities towards cancer cells than the second series. The mechanistic studies on two gold complexes by monitoring the cellular uptake showed the rapid cellular accumulation of the intact gold bis(NHC) and a good bioavailability, in good agreement with the antiproliferative activity of these two complexes. Moreover, both complexes inhibit TrxR, a common target for gold(I) complexes. The cell death induced by these two complexes was ROS-dependent. Besides anticancer activities, we also tested gold(I) mono-NHC complexes for other biomedical applications in parasite disease Leishmaniasis. They were screened in vitro against both promastigote and axenic amastigote forms of L. infantum. Moreover, their cytotoxicity was evaluated on the murine J774A.1 macrophages in order to determine their selectivity of action. Another topic of this thesis concerns iridium(III)-NHC complexes. Three families of theranostic iridium(III)-NHC complexes were prepared and characterized. The in vitro cytotoxicity of all the complexes against PC-3 prostate, T24 bladder cancer cells and non-cancerous NIH3T3 cells was evaluated. Moreover, all complexes are theranostic agents, and the confocal microscopy experiments of one complex showed that it can be quickly and effectively taken up into PC-3 cells and specifically localize into mitochondria. Interestingly, these complexes can act as efficient photosensitizers. The cytotoxicity of these complexes was increased substantially upon 365 nm light irradiation, which suggested the high potential to be mitochondria-targeting theranostic anticancer agents for photodynamic therapy
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TRASATTI, Andrea. "New heteroscorpionate and macrocyclic ligands, related metal complexes and novel Gold nanoparticles: synthesis, structure analysis and biological studies." Doctoral thesis, Università degli Studi di Camerino, 2013. http://hdl.handle.net/11581/401702.
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The synthesis, the structural and the biological analysis of a series of new macrocyclic, heteroscorpionate ligands and related copper complexes are reported in the first two parts of this PhD thesis. In the third part the study of the internalization processes of new gold nanoparticles in the HeLa cells were showed. In the first part the coordination environment and the stability behavior of the new macrocyclic ligands 1,10-dithia-4,7-diazacyclododecane-3,8-dicarboxylic acid (NEC-SE), 1,10-dithia-4,7-diazacyclotridecane-3,8-dicarboxylic acid (NEC-SP), 1,10-dithia-4,7-diazacyclotetradecane-3,8-dicarboxylic acid (NEC-SB), 4-methyl-1,7-ditihia-4,10,13-triazacyclopentadecane-9,14-dicarboxylic acid (NEC-SN-Me) and of the corresponding Cu(II) complexes were investigated both in the solid state and in aqueous solution. The Cu2+ complexation constants for NEC-SE were determined in aqueous solution. The behavior of the copper complexes in presence of the strong copper chelating bioagent human serum albumin was also examined, to gain information on the stability of these compounds in biological fluids. The corresponding 64Cu(II) labeled complexes were produced in major98% radiochemical purity in collaboration with Prof. J. S. Lewis (Memorial Sloan-Kettering Cancer Center, NY). Rats were injected with complexes and were euthanized at 1, 4 and 24 h. All three complexes were cleared from the blood over the first hour following injection but there was poor clearance of this activity over 24 h. In the second section the syntheses by direct coupling of preformed side chain acid and amine components of new nitroimidazole and glucosamine conjugated heteroscorpionate ligands, namely 2,2-bis(3,5-dimethyl-1H-pyrazol-1-yl)-N-(2-(2-methyl-5-nitro-1H-imidazol-1-yl)ethyl)acetamide (LMN) and 1,3,4,6-tetra-O-acetyl-2-{[bis(3,5-dimethyl-1H-pyrazol-1-yl)acetyl]amino}-2-deoxy-b-D-glucopyranose (LDAC), respectively, were reported. The related copper(II) complexes {[(LMN)2Cu]Cl2} and {[(LDAC)2Cu]Cl2} were prepared from the reaction of CuCl2*2H2O with LMN or LDAC in methanol solution. XAS and EXAFS were used to determine the local environment of the two copper(II) complexes. The new copper(II) complexes and the uncoordinated ligands were evaluated for their cytotoxic activity towards a panel of several human tumour cell lines. The results indicated that both copper(II) complexes show similar spectra of cytotoxicity and very low resistance factors (RF minus 2) against C13* ovarian cancer cells which have acquired resistance to cisplatin. In the last part only partial results were reported because the study is still in progress. This part of PhD work was carried out in collaboration with the research groups of Prof. Stellacci in the Department of Materials Science and Engineering, Ecole Polytechnique Federale de Lausanne (EPFL), Lausanne, Switzerland, during my abroad 6 months stage. The synthesis of a series of mixed-ligand gold nanoparticle (NPs) obtained varying the lengths of both the hydrophobic and hydrophilic ligand length were carried out. The synthesized NPs were studied using 1H-NMR (first and before the decomposition with potassium cyanide), TEM and GC-MS analysis. The NPs with a size between 4 and 10 nm were recovered using the fractionation by centrifugation, which is a technique that uses the principle that larger particles sediment faster than smaller ones. Confocal laser scanning microscopy (CLSM) and flow cytometry (FCM) were used to explore how the temperature of the system, the size of NPs and their shell composition affect the internalization processes in the analyzed cell.
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McDougald, Roy N. Jr. "Photochemical and Photophysical Properties of Mononuclear and Multinuclear Closed Shell D10 Coinage Metal Complexes and Their Metallo-organometallic Adducts." Thesis, University of North Texas, 2013. https://digital.library.unt.edu/ark:/67531/metadc407759/.
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This dissertation covers the studies of two major topics: the photochemistry of mononuclear and multinuclear gold(I) complexes and synthetic approaches to tailor photophysical properties of cyclic trinuclear d10 complexes. First a detailed photochemical examination into the photoreactivity of neutral mononuclear and multinuclear gold(I) complexes is discussed, with the aim of gold nanoparticle size and shape control for biomedical and catalysis applications. Next is a comprehensive systematic synthetic approach to tailor the photophysical properties of cyclic trinuclear d10 complexes. This synthetic approach includes an investigation of structure-luminescence relationships between cyclic trinuclear complexes, an examination into their π-acid/π-base reactivity with heavy metal cations and an exploration into the photophysical properties of new heterobimetallic cyclic trinuclear complexes. These photophysical properties inspections are used to screen materials for their employment in molecular electronic devices such as organic light-emitting diodes (OLEDs) and thin film transistors (OTFTs).
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Gutiérrez, Blanco Ana María. "Tetrametallic (Gold, Iridium and Rhaodium) complexes based on N-Heterocyclic carbenes. From luminescent properties to supramolecular assemblies." Doctoral thesis, Universitat Jaume I, 2021. http://dx.doi.org/10.6035/14104.2021.164087.
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The research carried out in this doctoral thesis can be summarized as the the preparation of different multimetallic complexes containing N-heterocylic carbene (NHC) ligands. In this aim, the main objective is to obtain new poly-NHC-based ligands with extended polyaromatic systems for the preparation of these complexes, which a combination of features that may give access to interesting photophysical and catalytic applications.La investigación llevada a cabo en esta Tesis doctoral puede resumirse como la preparación de diferentes complejos multimetálicos que contienen ligandos carbeno N-heterocíclico (NHC). Con este propósito, el objetivo principal es la obtención de nuevos ligandos basados en poli-NHC con sistemas poliaromáticos extendidos para la preparación de estos complejos, con una combinación de características que pueden dar acceso a aplicaciones fotofísicas y catalíticas muy interesantes.
Programa de Doctorat en Ciències
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Maity, Ayan. "Metal-Carbon (Metal = Iridium(III) and Gold(III)) Bond Formation Under Transmetalation and Catalytic Conditions; Metallonucleosides as Anticancer Drugs and Bio-photonic Probes; and Synthesis of Iridium Fluoride Complexes." Case Western Reserve University School of Graduate Studies / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=case1409924334.
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Weske, Sebastian. "From Copper to Gold: Identification and Characterization of Coinage-Metal Ate Complexes by ESI Mass Spectrometry and Gas-Phase Fragmentation Experiments." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2019. http://hdl.handle.net/21.11130/00-1735-0000-0005-12EA-F.
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Lee, Kwok-ming, and 李國明. "Synthesis, characterization and photophysical properties of chalcogenido, phosphinidene and alkynyl complexes of gold (I) and itscongener and their supramolecular assembly arising from metal--metalinteractions." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2011. http://hub.hku.hk/bib/B45983422.
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Upadhyay, Prabhat Kumar. "Design, Synthesis, and Characterization of Aqueous Polymeric Hybrid Composites and Nanomaterials of Platinum(II) and Gold(I) Phosphorescent Complexes for Sensing and Biomedical Applications." Thesis, University of North Texas, 2015. https://digital.library.unt.edu/ark:/67531/metadc822788/.
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The two major topics studied in this dissertation are the gold(I) pyrazolate trimer {[Au(3-R,5-R’)Pz]3} complexes in aqueous chitosan polymer and phosphorescent polymeric nanoparticles based on platinum(II) based complex. The first topic is the synthesis, characterization and optical sensing application of gold(I) pyrazolate trimer complexes within aqueous chitosan polymer. A gold(I) pyrazolate trimer complex, {[Au(3-CH3,5-COOH)Pz]3}, shows high sensitivity and selectivity for silver ions in aqueous media, is discussed for optical sensing and solution-processed organic light emitting diodes (OLEDs) applications. Gold(I) pyrazolate trimer complexes are bright red emissive in polymeric solution and their emission color changes with respect to heavy metal ions, pH and dissolved carbon dioxide. These photophysical properties are very useful for designing the optical sensors. The phosphorescent polymeric nanoparticles are prepared with Pt-POP complex and polyacrylonitrile polymer. These particles show excellent photophysical properties and stable up to >3 years at room temperature. Such nanomaterials have potential applications in biomedical and polymeric OLEDs. The phosphorescent hybrid composites are also prepared with Pt-POP and biocompatible polymers, such as chitosan, poly-l-lysine, BSA, pnipam, and pdadmac. Photoluminescent enhancement of Pt-POP with such polymers is also involved in this study. These hybrid composites are promising materials for biomedical applications such as protein labeling and bioimaging.
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Tang, Hau-san. "Design and synthesis of metal phosphine complexes of palladium(II) and gold(I) with various receptor ligands for ion-controlled or photoresponsive host-guest chemistry." Click to view the E-thesis via HKUTO, 2006. http://sunzi.lib.hku.hk/hkuto/record/B37877422.
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Tang, Hau-san, and 鄧巧珊. "Design and synthesis of metal phosphine complexes of palladium(II) andgold(I) with various receptor ligands for ion-controlled orphotoresponsive host-guest chemistry." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2006. http://hub.hku.hk/bib/B37877422.
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Santos, Jonnatan Julival dos. "Ouro: um metal multifuncional. Estudo das propriedades eletrônicas e espectroscópicas de suspensões e filmes de nanopartículas de ouro aplicados a sensoriamento." Universidade de São Paulo, 2013. http://www.teses.usp.br/teses/disponiveis/46/46136/tde-16012014-081808/.
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Nanopartículas de ouro são \"blocos de construção\" muito versáteis para a preparação de novos nanomateriais híbridos funcionais. Suas propriedades físico-químicas permitem a criação de sistemas capazes de absorver luz, transportar elétrons ou, ainda, interagir com moléculas e biomoléculas. Nesta tese foram estudados os fatores que influenciam o Espalhamento Raman Intensificado pela Superfície (SERS), visando o aumento da sensibilidade da técnica pela formação de compósitos com nanopartículas magnéticas, além de explorar a estratégia de montagem coordenativa para a preparação de nanomateriais híbridos contendo complexos de rutênio visando o desenvolvimento de sensores para moléculas e/ou íons moleculares. Assim, foi demonstrado como é possível aumentar o sinal de espalhamento Raman obtido em pelo menos 30%, através do controle da relação número de moléculas/ nanopartícula de ouro. Ou seja, verificou-se que a melhor relação sinal ruído foi alcançado com cerca de 16 mil moléculas de fenantrolina por nanopartícula de ~42 nm, gerando espectros mais definidos e sem a presença de bandas indesejáveis, por exemplo associadas aos agentes estabilizantes. Essa propriedade das nanopartículas de ouro foi potencializada por meio da associação com nanopartículas superparamagnéticas de óxido de ferro gerando substratos SERS sensíveis, reprodutíveis, de preparação simples e baratos. A interação entre as nanopartículas de ouro e as nanopartículas superparamagnéticas foram monitoradas por espectroscopia eletrônica no ultravioleta-visível, microscopias eletrônicas de varredura e de transmissão e microscopias de campo escuro e hiperespectral. Verificou-se que as nanopartículas interagem fortemente entre si gerando materiais supramoleculares que podem ser atraídas e concentradas utilizando-se um imã, para a realização de medidas de espectroscopia Raman/SERS. Essa nova metodologia e substrato SERS possibilitaram a quantificação de azul de metileno e de fenantrolina em concentrações na faixa de 5x10-9 a 5x10-11 mol dm-3. De fato, foi observado um aumento do sinal Raman de até 60 vezes, quando comparado ao sinal sem a concentração magnética. Finalmente, a interação das nanopartículas de ouro com três diferentes clusters trigonais de acetato de rutênio (ou, simplesmente, clusters de rutênio) simétricos, com os ligantes 4-cianopiridina, 4,4\'-bispiridina e trans-1,2-bis(4-piridil)etileno como substituintes axiais foi explorado para a preparação de polímeros de coordenação funcionais. Os clusters de rutênios foram caracterizadas por espectroscopia eletrônica no ultravioleta-visível, eletroquímica e espectroeletroquímica. A seguir os clusters de rutênio foram utilizados como \"réguas molecular\", explorando a diferença de tamanho e o fato delas funcionarem como \"moléculas-pontes\", para a realização de estudos de acoplamento plasmônico, acompanhando-se tal fenômeno por espectroscopia eletrônica no ultravioleta-visível. A interação entre as nanopartículas de ouro e os clusters de rutênio puderam ser estudadas por espectroscopia de ressonância plasmônica de superfície (SPR), onde foi investigado o processo de formação de filmes por meio da técnica. Estes foram caracterizados por espectroscopia Raman utilizando lasers de excitação de 532 e 785 nm, onde foram observados as bandas vibracionais dos clusters de rutênio e as contribuições ressonante, eletromagnética e de transferência de cargana intensificação Raman. Esses nanomateriais híbridos foram ainda imobilizados sobre eletrodos de vidro condutor e utilizados como sensores eletroquímicos para detecção de nitrito na faixa de concentrações entre 0,5x10-6 e 1x10-3 mol dm-3.Gold nanoparticles are \"building blocks\" very versatile for the preparation of new functional hybrid nanomaterials . Their physicochemical properties allow the creation of systems capable of absorbing light, electron transportation, or even interact with molecules and biomolecules. In this thesis we studied the factors that influence the surface enhanced Raman scattering (SERS), in order to increase the sensitivity of the technique by forming composites with magnetic nanoparticles, as well as explore the coordinative assembly strategy for the preparation of hybrid nanomaterials containing complexes ruthenium for the development of sensors for molecules and/or molecular ions . Thus, it was shown how is possible to increase the Raman signal obtained by at least 30 % just controlling the relative number of molecules/gold nanoparticle. That is, it was found that the best signal to noise ratio was achieved with about 16 thousand of molecules per nanoparticle ~ 42 nm, more defined and generating spectra without the presence of undesirable bands, for example, associated with stabilizers. This property of gold nanoparticles was enhanced by association with superparamagnetic nanoparticles of iron oxide generating sensitive SERS substrates, reproducible, with simple preparation methodology and inexpensive. The interaction between the gold nanoparticles and superparamagnetic nanoparticles were monitored by electronic spectroscopy in the ultraviolet -visible, scanning electron microscopy and transmission electron microscopy and dark field and hyperspectral microscopy. It was found that the nanoparticles interact strongly which can be attracted and concentrated using a magnet for the realization of Raman spectroscopy measurements / SERS. This new methodology, and SERS substrate, allowing the quantification of methylene blue concentrations and phenantroline in the range of 5x10-9 to 5x10-11 mol dm-3. In fact , we observed an increase in the Raman signal up to 60 times when compared to the signal without the magnetic concentration. Finally, the interaction of gold nanoparticles with three different clusters trigonal ruthenium acetate (or simply ruthenium clusters) symmetrical with the ligand 4- cyanopyridine, 4,4\'-bispiridina and trans-1,2-bis(4-pyridyl) ethylene axial been explored as substituents for the preparation of functional coordination polymers. Ruthenium Clusters were characterized by electron spectroscopy in the ultraviolet-visible, electrochemical and spectroelectrochemical. After that, the ruthenium clusters were used as \"molecular rulers\", exploring the size difference and the fact that they can act as \" molecules-bridges \" for studies of plasmon coupling, following up this phenomenon by electronic spectroscopy in the ultraviolet - visible. The interaction between the gold nanoparticles and ruthenium clusters could be studied by spectroscopy, surface plasmon resonance (SPR), where it investigated the process of formation of films by the technique. These were characterized by Raman spectroscopy using laser excitation of 532 and 785 nm, which were observed vibrational bands of ruthenium clusters and contributions resonant electromagnetic and transfer cargana Raman enhancement. These hybrid nanomaterials were also immobilized on glass electrodes and conductive used as electrochemical sensors for the detection of nitrite concentrations in the range of 0.5 x10-6 to 1x10-3 mol dm-3.
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Atoini, Youssef. "New luminescent hybrid materials : synthesis and properties." Thesis, Strasbourg, 2017. http://www.theses.fr/2017STRAF004/document.
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L'objectif de cette thèse est la synthèse, la caractérisation et l'étude de complexes métalliquesluminescents, en particulier de Pt (II), leurs propriétés d'agrégation en solution, mais également dansun espace confiné ainsi qu’en surface. L'incorporation de complexes de métaux de transition dans lastructure poreuse, et ainsi que leur dépôt à la surface de nanoparticules et dans un cadre métalloorganique(MOF), par greffage post-synthétique, ont été étudiés. Sont également étudiés lacorrélation entre les propriétés de films d’une série de complexes de Pt(II) avec leur morphologie,leur mobilité électronique et la simulation de leur structure auto-assemblée par diffraction auxrayons-X. Les propriétés de luminescence de complexes amphiphiles de Pt(II) sont améliorées àl’intérieur de nanoparticules de silice mesoporeuse par la création d’un d’espace confiné. Un effetsimilaire est observé par le dépôt de complexes de Pt(II) fonctionnalisés sur une surface denanoparticules d’or. La luminescence d’un cadre organométallique a été modifiée par greffage postsynthétiquede complexes d’Ir(III) et de Pt(II)The aim of this thesis is the synthesis, characterization and investigation of luminescent metalcomplexes, and in particular of Pt(II) compounds, their aggregation properties in solution but inconfined space as well. The incorporation of transition metal complexes in porous structure, and inparticular in a metal-organic framework (MOF), by post-synthesis grafting, have been investigated.Luminescence properties of amphiphilic Pt(II) complexes were enhanced inside mesoporous silicananoparticles by the creation of a confined space. Similar effect is observed by deposition offunctionalized Pt(II) complexes on gold nanoparticles surface. Luminescence of metal organicframework was tuned by post-synthetic grafting of Ir(III) and Pt(II) complexes
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Weske, Sebastian [Verfasser], Konrad [Akademischer Betreuer] Koszinowski, Konrad [Gutachter] Koszinowski, and Franc [Gutachter] Meyer. "From Copper to Gold: Identification and Characterization of Coinage-Metal Ate Complexes by ESI Mass Spectrometry and Gas-Phase Fragmentation Experiments / Sebastian Weske ; Gutachter: Konrad Koszinowski, Franc Meyer ; Betreuer: Konrad Koszinowski." Göttingen : Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2020. http://d-nb.info/1202605028/34.
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Tugny, Coralie. "Application of the metal-catalyzed rearrangement of propargyl acetates to the total synthesis of natural products of the neomerane family : application in catalysis of new secondary phosphine oxide- and NHC-capped cyclodextrin-gold(I) complexes." Thesis, Paris 6, 2015. http://www.theses.fr/2015PA066607.
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L'étude des petites molécules naturelles apporte continuellement de nouvelles connaissances en chimie organique et a un impact certain sur la recherche biomédicale. Les réactions catalysées par des métaux de transition ont fréquemment été utilisées dans des étapes clés vers la synthèse de produits naturels. En particulier au cours de la dernière décennie, l'or a été de plus en plus utilisé en catalyse homogène pour effectuer ces transformations. Le présent travail a pour objectif la valorisation en synthèse totale du réarrangement des acétates propargyliques catalysé par l'or. La (±)-Valénéomérine B et le (±)-Néoméranol sont deux produits naturels de la famille des Néoméranes dont nous avons envisagé la synthèse via la préparation d'un intermédiaire commun issu du réarrangement d'un acétate propargylique catalysé à l'or. Parallèlement, le comportement de nouveaux complexes d'or(I) à base d'oxides de phosphines secondaires et de cyclodextrines a été étudié dans le but de mieux contrôler la sélectivité des réactions catalysées à l'orThe study of small molecule natural products provides some knowledge about organic chemistry and has an impact on biomedical research. Transition metal-catalyzed reactions have been frequently used to affect key transformations. Especially, there has been a noticeable trend during the past decade towards the use of homogeneous gold-catalyzed transformations. This work aims at the valorization of the gold-catalyzed rearrangement of propargyl acetates in the total syntheses of (±)-Valeneomerin B and (±)-Neomeranol. These compounds are sequiterpenoid natural products, the synthesis of which has been envisioned from the preparation of a common intermediate resulting from the gold-catalyzed rearrangement of a propargyl acetate precursor. At the same time, the behaviour of new secondary phosphine oxide- and CNHC-capped cyclodextrin-gold(I) complexes has been studied, to try and achieve better control on the course of gold-catalyzed transformations
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Loret, Jean-François. "Extraction de metaux precieux par des gels organiques." Université Louis Pasteur (Strasbourg) (1971-2008), 1987. http://www.theses.fr/1987STR13068.
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Preparation de gels qui sont des polymeres reticules qui gonflent lorsqu'ils sont plonges dans des solvants adequats. Le gel pvc-tbp est utilise pour extraire l'or en milieu hcl : les ions m(cn)::(2)**(-) (m=ag,au) en milieu koh sont extraits par le gel dcy-18c6-chcl::(3)-br (br = polylentadiene)
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Zhu, Mingxin. "Syntheses, characterization and photophysical properties of platinum(II) and gold(I) complexes containing ortho- and meta-oligo(phenyleneethynylene) ligands." View the Table of Contents & Abstract, 2008. http://sunzi.lib.hku.hk/hkuto/record/B39570757.
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朱明新 and Mingxin Zhu. "Syntheses, characterization and photophysical properties of platinum(II) and gold(I) complexes containing ortho- and meta-oligo(phenyleneethynylene) ligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2008. http://hub.hku.hk/bib/B39707325.
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De, Jongh Leigh-Anne. "Imine-donor complexes with group 6 and group 11 transition metals : coordination and dynamics." Thesis, Stellenbosch : Stellenbosch University, 2008. http://hdl.handle.net/10019.1/2001.
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Thesis (MSc (Chemistry and Polymer Science))--Stellenbosch University, 2008.In this study the coordination of ligands with several coordination sites, 2-aminoazoles (2- amino-4-methylthiazole), 2-aminobenzothiazole, 2-aminobenzoimidazole and 2- aminothiazoline and a biguanidine (N-(2-methylphenyl)imidodicarbonimidic diamide) to soft metal centres [gold(I) (group 11), chromium(0) (group 6) and tungsten (0) (group 6)] was investigated. The aminoazoles have three coordination sites, an exocyclic amine nitrogen, an endocyclic imine nitrogen and an endocyclic thioether sulphur. The biguanidine ligand has three sites for deprotonation, one central amine and two imine nitrogens, and at least five sites available for nitrogen coordination.
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Hickey, James Laurence. "Synthetic approaches towards gold (I) and silver (I) complexes of functionalised N-heterocyclic carbene ligands." University of Western Australia. School of Biomedical, Biomolecular and Chemical Sciences, 2009. http://theses.library.uwa.edu.au/adt-WU2009.0090.
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This work focuses on the design and synthesis of Au(I) and Ag(I) complexes from ligand systems that aim to combine both N-heterocyclic carbene (NHC) and phosphine ligand types. A number of synthetic approaches towards both the ligands and the prepared metal complexes have been developed, with a concerted effort on achieving the desired Au(I) or Ag(I) complexes with minimal reaction steps and synthetic style. The thesis body is divided into two main sections. The first section addresses the preparation of suitable ligand precursors of potential Au(I) and Ag(I) complexes in the form of halo- and phosphino-functionalised imidazolium salts. Several series of haloalkylimidazolium salts were prepared that encompass a range of halogens (Cl, Br, I), alkyl substituents (Me, i-Pr, t-Bu, n-Bu), differing alkyl linker length (n = 0-3), and a variety of organic spacers employed to bridge multi-imidazolium moieties. Novel bidentate and multidentate phosphinoalkylimidazolium salts were synthesised from the various haloalkylimidazolium salts, via the substitution of a halide with nucleophilic diphenylphosphide. A new approach towards rare methylene bridged phosphinomethylimidazolium salts was achieved from the reactions of halomethylimidazolium salts with diphenylphosphine. The second section investigates the preparation of Au(I) and Ag(I) complexes from the halo- and phosphino-functionalised imidazolium salts. A series of dicationic 10, 12, and 14-membered metallacyclic Ag(I) complexes were prepared from the bidentate phosphinoalkylimidazolium salts. The dinuclear Ag(I) metallacycles combine two phosphino-functionalised NHC ligands that are bridged by two coordinated Ag(I) ions in an exclusively head-to-head arrangement. A dinuclear Ag(I) metallacycle was investigated for transmetallation potential to a Au(I) complex and found to selectively transmetallate at the Ag(I) coordinated to the NHC ligands to form a bimetallic metallacycle. Unexpected phosphine oxidation of a 10-membered dinuclear Ag(I) metallacycle resulted in complex disproportionation to an isolable and rare silver(I) trimer. Metal-NHC complexes from haloalkylimidazolium salts have not been reported previously, a novel approach to the synthesis of a series of Au(I) complexes from haloalkylimidazolium salts and a respective gold source was developed and is reported herein. Different synthetic approaches towards Au(I) complexes with the phosphinoalkylimidazolium salts explored a variety of ways to generate the NHC from an imidazolium in the presence of the phosphine. A one-pot, high yielding synthesis of a dinuclear Au(I) complex from PPh3 was also devised, with controlled assembly of the complex resulting in a similar head-to-head ligand arrangement to the dinuclear Ag(I) metallacycles. As an aside, a family of mononuclear [Au(R2NHC)2]+ complexes (R = Me, i-Pr, t- Bu, n-Bu, Cy) prepared previously in our research group, was expanded because of the promising antimitochondrial activity shown by [Au(i-Pr2NHC)2]+. Two new [Au(R2NHC)2]+ complexes with simple alkyl chain functionality were prepared with fine-tuned lipophilicity in close proximity to that of [Au(i-Pr2NHC)2]+.
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Frank, Nicolas. "d10-Metallkomplexe des p-tert-Butyltetramercaptotetrathiacalix[4]arens." Doctoral thesis, Humboldt-Universität zu Berlin, 2020. http://dx.doi.org/10.18452/21975.
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Ziel dieser Arbeit war es, das Potenzial von p-tert-Butyltetramercaptotetrathiacalix[4]aren (H4(MTC[4])) zum Aufbau von mehrkernigen Komplexen mit weichen Metallionen mit d10-Elektronenkonfiguration zu untersuchen. H4(MTC[4]) bietet im Vergleich zum bekannteren p-tert-Butylcalix[4]aren erweiterte Bindungsmöglichkeiten für Metallionen an den Thioetherbrücken. Die Funktion der Metallionen Cu(I) und Zn(II) in biologischen Systemen lieferte die anfängliche Inspiration, jedoch erschien auch die Untersuchung anderer Metalle wie Nickel, Silber und Gold in Verbindung mit (MTC[4])4- Liganden lohnenswert, da diese Metalle durch ihre jeweils bevorzugten Koordinationsgeometrien neue Strukturen und Koordinationsmöglichkeiten an H4(MTC[4]) aufzeigen könnten.
In Experimenten mit Kupfer(I)-Ionen konnten der Kupferkomplex [(Ph3PCu)4(MTC[4])] sowie das Hexamer [Cu4(MTC[4])]6 hergestellt und charakterisiert werden. [Cu4(MTC[4])]6 weist eine einzigartige, supramolekulare, hohle Cu24S48-Käfigstruktur auf. Die [Cu4(MTC[4])]-Einheiten werden durch Cu2S2-Motive verknüpft, die extrem kurze Cu···Cu-Abstände aufweisen. Durch NMR-Experimente wurde gezeigt, dass die Hohlräume von [Cu4(MTC[4])]6 in Lösung Acetonitril und Methan aufnehmen können.
In Experimenten mit Silber(I)-Ionen wurden die Molekülstrukturen der Silberkomplexe [(Ph3PAg)2AgH(MTC[4])], [(Ph3PAg)4AgCl(MTC[4])] und [(Ph3PAg)4(MTC[4])] bestimmt. Diese zeigen, dass H4(MTC[4]) gegenüber Silber- und Kupferionen ein ähnliches Koordinationsverhalten aufweist.
In Experimenten mit Gold(I)-vorläufern war es möglich, zu steuern, wie viele Metallionen ein einzelnes Molekül H4(MTC[4]) koordiniert. Die Komplexe [(Ph3PAu)2H2(MTC[4])], [(Me3PAu)3H(MTC[4])] und [(Me3PAu)4TlCl(MTC[4])] wurden synthetisiert. Diese bieten teilweise durch vorhandene freie Thiolfunktionen Potenzial für die Synthese heterometallischer Komplexe.It was the aim of this work, to assess the potential of p-tert-Butyltetramercaptotetrathiacalix[4]arene (H4(MTC[4])) to create multinuclear complexes with soft metal ions of d10 electron configuration. In contrast to the more known p-tert-Butylcalix[4]aren, H4(MTC[4]) offers extended possibilities for the coordination of metal ions at the thioether groups. While this work was initially inspired by the function of Cu(I) and Zn(II) ions in biological systems, the metal ions, which were incorporated into the Calixarene, were soon expanded by Ni(II), Ag(I) and Au(I) ions. Through their different preferred coordination geometries, these metal ions could yield new information about coordination modes of H4(MTC[4]). In experiments with copper(I) ions the complex [(Ph3PCu)4(MTC[4])] and the hexamer [Cu4(MTC[4])]6 were synthesized and characterized. [Cu4(MTC[4])]6 consists of a unique, supramolecular hollow Cu24S48 cage structure. The [Cu4(MTC[4])] units are connected by Cu2S2 motivs, which display extraordinary short Cu···Cu distances. An investigation by NMR spectroscopy indicated that the cavities of [Cu4(MTC[4])] in solution can hold acetonitrile or methane molecules. In experiments with silver(I) ions, the molecular structures of the compounds [(Ph3PAg)2AgH(MTC[4])], [(Ph3PAg)4AgCl(MTC[4])] and [(Ph3PAg)4(MTC[4])] were determined. In these compounds H4(MTC[4]) exhibits a similar coordination behaviour towards Ag(I) ions as it does towards Cu(I) ions. In experiments with gold(I) precursors it was possible to control how many gold(I) ions were coordinated by H4(MTC[4]). The complexes [(Ph3PAu)2H2(MTC[4])], [(Me3PAu)3H(MTC[4])] and [(Me3PAu)4TlCl(MTC[4])] were synthesized and studied. Due to their free thiol functions, they are potential precursors for the synthesis of heterometallic complexes.
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Theulier, Cyril Alexis. "Ligands ambiphiles et coopérativité métal - acide de Lewis." Thesis, Toulouse 3, 2021. http://www.theses.fr/2021TOU30013.
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Cette thèse porte sur l'étude de la coopérativité métal/acide de Lewis. L'or se distingue des autres métaux de transitions par une réticence à s'engager dans les étapes élémentaires classiquement rencontrées en chimie organométallique. Ce projet de recherche repose sur la coordination de l'or par des ligands ambiphiles permettant l'installation d'un acide de Lewis dans la sphère de coordination. L'objectif ici est de tirer profit de la proximité de l'accepteur pour exalter la réactivité de l'or et réaliser des transformations initialement défavorables. Le premier chapitre aborde de manière très générale l'état de l'art de la chimie organométallique de l'or. Une attention particulière est portée aux limitations générées par une difficulté intrinsèque de ce métal à accéder à de hauts degrés d'oxydations. La coordination des ligands ambiphiles sur l'or y est introduite dans un second temps. La relation entre les divers modes de coordinations adoptés et la réactivité des complexes résultant a été mise en avant. Le deuxième chapitre est consacré à la synthèse de nouveaux complexes d'or PB-Au(I)-R comportant un co-ligand organique. Ces derniers ont été obtenu depuis des précurseurs aryle, méthyle et trifluorométhyle d'Au(I) par coordination d'une phosphine borane récemment décrite par l'équipe et présentant un fragment borane hautement acide de Lewis. La présence d'une interaction datives de l'or vers le bore a pu être établi. L'évaluation de la force de l'interaction Au→B a notamment permis de discuter le caractère sigma-accepteur du nouveau ligand. L'addition oxydante de divers électrophiles a ensuite été étudiée. Lors l'exploration de la réactivité des complexes PB-Au(I)-R (R = vinyle, acétylènyle), une réaction de 1,1-phosphaboration stéréo- et régiosélective du groupement insaturé a été découverte et fera l'objet d'un troisième chapitre. Des complexes zwittérioniques issus de l'abstraction du groupement organique de l'or vers le bore ont été identifiés comme intermédiaire clé de la transformation. Le mécanisme de la réaction a fait l'objet d'une étude expérimentale et théorique mettant en évidence une action concertée du bore et de l'or. Enfin, il a été démontré dans un dernier chapitre que la coordination des mono-phosphines boranes sur les complexes d'Au(III) favorise grandement l'élimination réductrice C(sp3)-C(sp3) connue pour être difficile. Des études cinétiques montrent un impact de la présence de l'acide de Lewis. L'étude par DFT du mécanisme soutient la participation du borane des ligands ambiphilesThe present work is dedicated to the study of metal/Lewis cooperativity. Over years gold has proven its reluctance to undergo elementary steps classicaly disclosed in the coordination chemistry of transition metals. The initial concept behind this research project consist in the installation of a Lewis acid in the first coordination sphere through the coordination of ambiphilic ligands. The ultimate objective is to take full advantage of the assistance provided by the acceptor to extol the reactivity at gold and achieve challenging transformations. The introductive chapter delivers a bibliographic overview of the organometallic chemistry encountered with gold. A peculiar interest is paid to the limitations araising from an intrinsic difficulty to access high oxidation state. The coordination chemistry of ambiphilic ligands is subsequently introduced. The relation between the coordination mode of the ligand and the reactivity of the ensuing complexe is highlighted. To support this research a new mono-ortho-phenylene-phosphinoborane bearing an extremely Lewis acidic boron has been developed. The second chapter brings forward the synthesis of neutral species by coordination of the ambiphilic ligand on gold(I) aryl, methyl and trifluoromethyl complexes. The presence in those species of a gold to boron dative interaction (Z interaction) allowed to assess and discuss the sigma-acceptor ability of the new ligand. Then their reactivity towards oxidative addition has been studied. The third chapter results from a serendipitous discovery made over attemts to generalize the former reactivity. The phosphine borane was found to react with gold(I) alkynyl and alkenyl complexes. via a stereo and regioselective 1,1-phosphaboration process. Zwitterionic complexes stemming from a migration of the organic fragment from the gold to the boron have been authenticated as key intermédiates. Kinetic and DFT investigations suggest a stepwise pathway including the decoordination of the phosphine followed by the anti nucleophilic attack to the unsaturated bond henceforth activated by gold. The boron center acts as a relay and tether for the organic moiety. The last chapter is devoted to the Au(III)/Au(I) reductive elimination. The complexation of a mono-ortho-phenylene-phosphinoborane has shown to foster the challenging C(sp3)-C(sp3) reductive coupling. Kinetic studies emphasised a strong impact of the ligand's Lewis acidity supporting the participation of the acceptor in the mechanism. DFT calculations were performed to elucidate the mechanism and shed light onto a gold/Lewis acid cooperativity