Dissertationen: „Novel Transition Metal Complexes“

1

Veighy, Clifford Robert. „Novel cyclopentadienyl transition metal complexes“. Thesis, University of Southampton, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.327366.

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2

Blunden, Ralph Benedict. „Novel early transition metal cyclopropenyl complexes“. Thesis, University of Sussex, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.360552.

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3

Dossett, David Michael. „The synthesis of novel chiral transition metal complexes“. Thesis, University of Southampton, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.402060.

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4

Cairns, Gareth Alan. „Novel aspects of alkyne substituted transition metal complexes“. Thesis, University of Bath, 1998. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.242813.

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5

Mayo, Richard Andrew. „Transition-metal derivatives of phosphine, arsine and stibine“. Thesis, University of Edinburgh, 1986. http://hdl.handle.net/1842/15303.

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6

Blincko, Stuart. „Novel luminescent compounds for immunoassay“. Thesis, City University London, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.255249.

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7

Lu, Canzhong. „Novel transition metal complexes of sterically hindered silyl thiolate ligands“. Thesis, University of Essex, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.307857.

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8

Green, Simon Michael. „The synthesis and application of novel chiral transition metal complexes“. Thesis, University of Southampton, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.285879.

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9

Yoo, Hyunsuk S. M. Massachusetts Institute of Technology. „Synthesis and mechanistic studies of novel antitumor transition metal complexes“. Thesis, Massachusetts Institute of Technology, 2014. http://hdl.handle.net/1721.1/91121.

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Thesis: S.M. in Inorganic Chemistry, Massachusetts Institute of Technology, Department of Chemistry, 2014.
Cataloged from PDF version of thesis. Vita.
Includes bibliographical references.
In order to overcome side effects and drug resistance associated with conventional Pt(II) drugs, our lab has developed novel platinum complexes. One of the new platinum complexes developed in our lab is the monofunctional platinum anti-cancer compound phenanthriplatin. We have found that by binding to sulfur complexes, phenanthriplatin undergoes changes in its kinetic and cytotoxic properties. Sulfur adducts of phenanthriplatin were synthesized to study the complex roles sulfur compounds serve in the cellular action of the monofunctional compound. In addition, we have examined how Pt(IV) chemistry can be successfully applied to increase the efficacy of Pt(II) compounds. We conjugated hydrophobic chains to trans-[Pt(NH₃)₂Cl₂] (TDDP) through isocyanate couplings and successfully transformed TDDP into an active compound. We demonstrated that Pt(IV) chemistry can be applied to transform even inactive trans compounds into active complexes that can potentially be used in chemotherapy. Finally, we examined the anticancer properties of the dinuclear osmium(VI) nitrido complex [NBu₄]₂[(OsNCl₄)₂(pyz)]. We studied its cellular activity in the hope of discovering interesting and unexpected properties. We found that the compound has moderate cytotoxicity and leads to DNA damage and apoptosis.
by Hyunsuk Yoo.
S.M. in Inorganic Chemistry

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10

Smith, Charles J. „Transition metal complexes on novel, polydentate, water-soluble, phosphine ligands /“. free to MU campus, to others for purchase, 1997. http://wwwlib.umi.com/cr/mo/fullcit?p9841335.

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11

Williams, Charlotte Katherine. „Novel ferrocenediyl ligands, their transition metal complexes and potential for catalysis“. Thesis, Imperial College London, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.246677.

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12

Westbrook, Georgina. „Synthetic and electrochemical studies of novel transition metal and lanthanide complexes“. Thesis, University of Nottingham, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.436811.

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13

Porter, Robin Mark. „Novel amido / imino, diamido / ether and phenoxyimine early transition metal complexes“. Thesis, University of Southampton, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.409611.

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14

McKenzie, Luke Kagiso. „Novel transition metal complexes for use as photosensitizers in photodynamic therapy“. Thesis, University of Sheffield, 2017. http://etheses.whiterose.ac.uk/19554/.

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Herein, the exploration of a range of novel TM complexes for use as PS in the PDT of cancer is reported. Novel small-molecule TM complexes of Pt(II), Os(II) and Ir(III) metal centres were explored. Their photophysical characteristics, such as wavelength of activation and singlet oxygen yields, were assessed for suitability as PS before cellular uptake and toxicity in the dark was determined. Compounds showing favourable cellular uptake and toxicity upon initial screening were explored further. An iridium complex (IrNew) emerged as the most promising PS candidate showing high PS activity and low dark toxicity in a number of cancer cell lines. The mitochondrial localisation and apoptotic mode of cell death of IrNew was determined. With a high photo-toxicity index (up to > 555) at low light doses (3.6 J cm-2) the reported compound is a promising candidate but the need for relatively short wavelength light (405 nm) to activate the compound would severely limit its clinical use. As such alternative modes of activation were explored. An alternative to one-photon activation in PDT is two-photon activation allowing PS activation in the NIR. IrNew, in combination with NIR light (λexc = 760 nm), led photo-induced cell death in cell monolayers (HeLa) clearly demonstrating the potential of IrNew as a two-photon activated PS. The use of 3D oral cancer models as a tool for investigation of tissue effects in PDT were developed for the first time. While two- photon activation offers PS activation in the NIR, the requirement for high power lasers has hindered its clinical application. As an alternative, lanthanide upconverting nanoparticles which can transform two photons of near-infrared (NIR) light into a photon of UV/Vis light to activate the photosensitizer were successfully synthesised. These particles represent potential future treatment modality in the development of continuous wave NIR PDT.

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15

Fujita, Kenichi. „Synthesis, Structure, and Reactivity of Novel Group 8 Transition Metal Complexes“. Kyoto University, 1997. http://hdl.handle.net/2433/202318.

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Kyoto University (京都大学)
0048
新制・課程博士
博士(工学)
甲第6878号
工博第1629号
新制||工||1070(附属図書館)
15965
UT51-97-H262
京都大学大学院工学研究科物質エネルギー化学専攻
(主査)教授光藤武明, 教授植村榮, 教授玉尾皓平
学位規則第4条第1項該当

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16

Monticelli, Marco. „Novel di(n-heterocyclic carbene) ligands and related transition metal complexes“. Doctoral thesis, Università degli studi di Padova, 2017. http://hdl.handle.net/11577/3422292.

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In the last decades, N-heterocyclic carbenes (NHC) ligands have been studied by many groups due to their peculiarity in terms of major stability and versatility with respect to other type of ligands based on nitrogen (amines, imines, etc.) or phosphorous (phosphines, phosphites, etc.) donor atoms. Nowadays, the role of these ligands in the chemistry of transition metal complexes is pivotal, and the applications of the resulting compounds span from catalysis to luminescence to bioinorganic chemistry. This PhD, a collaboration between the University of Padova and the University of Strasbourg, is focused on the chemistry of di(N-heterocyclic carbene) ligands and can be divided in four families of ligands that constitute the four chapters: i) metal complexes with di(N-heterocyclic carbene) ligands bearing a rigid phenylene bridge between the carbene units; ii) metal complexes combining an imidazole-based NHC ligand functionalized with a triazole in the 5 position of the backbone; iii) metal complexes with heteroditopic ligands based on imidazol-2-ylidene and 1,2,3-triazol-5-ylidene moieties connected with a propylene bridge; iv) bis(benzoxazolium) proligands and attempted synthesis of related transition metal complexes. i) Metal complexes with di(N-heterocyclic carbene) ligands bearing a rigid phenylene bridge between the carbene units. Ortho- meta- and para-phenylene bis(imidazolium) salts have been used as proligands for the syntheses of various silver(I) complexes. These compounds, with general formula [Ag2L2](PF6)2 (L=di(N-heterocyclic carbene) ligand), have been used as transmetalating agents for the formation of the corresponding gold(I) and copper(I) complexes. These compounds maintain the same dinuclear dicationic molecular structure as for the silver(I) precursors, as confirmed by the resolved solid state crystal structures. The photoluminescence properties of the synthesized complexes have been studied and are strongly influenced by the structure of the di(NHC) ligand employed. In particular, the gold(I) complexes show interesting quantum yields of emission modulated by the geometry of the complex (distance between the two metal centers) and also by the packing of the complexes in solid state. With the ortho-phenylene silver(I) diNHC complex, the transmetalation was also successful for the access to mononuclear ruthenium(II) and iridium(III) complexes that show a chelate coordination of the ligand on the metal center. ii) metal complexes combining an imidazole-based NHC ligand functionalized with a triazole in the 5 position of the backbone. The copper catalyzed azide alkyne cycloaddiction reaction (CuAAC) also called “click reaction” has been used for the functionalization of the [5-(trimethylsilyl)ethynyl]-1-methylimidazole with a 1,2,3-triazole ring. As function of the methylating agents, it was possible to alkylate only the nitrogen on the imidazole ring (proligand i) or both on imidazole and triazole rings (proligands l and m). Starting from the proligands l and m, silver(I) complexes of stoichiometry Ag:L 1:1 (L=di(N-heterocyclic carbene) ligand) have been obtained, albeit with poor purity due to the oily nature of the products. Using the proligand i it has been possible to isolate a silver(I) complex of formula AgCl(NHC), which has been successively employed for the synthesis of gold(I), copper(I) and ruthenium(II) complexes. The in vitro cytotoxic activities of these compounds have been evaluated and in these preliminary results the silver(I) complex appears the most active and selective. iii) metal complexes with heteroditopic ligands based on imidazol-2-ylidene and 1,2,3-triazol-5-ylidene moieties connected with a propylene bridge. Heteroditopic proligands have been successfully synthesized using the CuAAC click reaction followed by methylation and anion exchange. A series of novel di-NHC gold(I) complexes, having general formula [Au2L2](PF6)2, have been synthesized and fully characterized through the transmetalation of the di-NHC moiety from pre-formed silver(I) complexes. The same pathway has been adopted for the synthesis of palladium(II) complexes that show the chelation of two ligands on the same metal center (i.e. homoleptic complexes). Due to the presence of two different carbene units (imidazole-2-ylidene and triazol-5-ylidene), it is possible to obtain a mixture of isomers which has been investigated by NMR and mass analyses. iv) bis(benzoxazolium) proligands and attempted synthesis of related transition metal complexes. Finally the chemistry of benzoxazole has been investigated. Different proligands containing benzoxazole rings have been synthesized starting from the corresponding diamine. These organic scaffolds have been used as proligands for the synthesis of metal complexes. Unfortunately, despite the various reaction conditions adopted (deprotonating agent, solvent, temperature, time...), the results obtained in this regard are not satisfactory, probably for the intrinsic instability of the ligand precursors and/or of the corresponding free carbenes.
Nelle ultime decadi, i leganti carbenici N-eterociclici sono stati studiati da numerosi gruppi in virtù delle loro peculiarità, quali maggiore stabilità e versatilità rispetto a leganti con atomi donatori all’azoto (ammine, immine etc.) o al fosforo (come per esempio fosfine, fosfiti ed altri). Attualmente, il ruolo di questi leganti nella sintesi di complessi con metalli di transizione è essenziale e le applicazioni dei corrispondenti complessi spaziano dalla catalisi alla luminescenza fino alla chimica bioinorganica. Questo dottorato, effettuato in collaborazione tra l’Università degli Studi di Padova e l’Università di Strasburgo, è focalizzato sulla chimica dei carbeni N-eterociclici e può essere diviso in quattro differenti capitoli: i) complessi metallici con leganti dicarbenici N-eterociclici legati da ponte fenilene rigido; ii) complessi metallici con legante carbenico N-eterociclico funzionalizzato con un triazolo in posizione 5 del backbone; iii) complessi metallici con leganti eteroditopici basati su unità imidazol-2-ilideniche e triazol-5-ilideniche legate tra loro mediante ponte propilenico; iv) leganti bis(benzossazolici) e tentativi di sintesi dei corrispondenti complessi con metalli di transizione. i) complessi metallici con leganti dicarbenici N-eterociclici legati da ponte fenilene rigido. Complessi di argento(I) sono stati sintetizzati partendo dai sali precursori dei leganti bisimidazolici con ponte orto- meta- e para-fenilenico. Tali complessi, con formula generale [Ag2L2](PF6)2 (L = legante dicarbenico N-eterociclico), sono stati usati come agenti di transmetallazione per l’ottenimento dei complessi di oro(I) e rame(I) corrispondenti; questi composti mantengono la medesima natura dinucleare dicationica dei precursori di argento, confermata dalla risoluzione delle strutture mediante diffrazione ai raggi X. Le proprietà di luminescenza dei complessi sintetizzati sono state studiate e sono fortemente influenzate dalla struttura del legante dicarbenico N-eterociclico utilizzato. In particolare i complessi di oro(I) presentano interessanti rese quantiche di emissione che variano a seconda della geometria del complesso (in termini di distanza tra i centri metallici) e soprattutto per il packing dei complessi allo stato solido. A partire dal complesso di argento con legante dicarbenico a ponte orto-fenilene, la reazione di transmetallazione è stata utilizzata per la sintesi di complessi mononucleari di rutenio(II) e iridio(III) che mostrano la chelazione dell’unità dicarbenica al centro metallico. ii) complessi metallici con legante carbenico N-eterociclico funzionalizzato con un triazolo in posizione 5 del backbone. La reazione di cicloaddizione azide alchino rame catalizzata (CuAAC) comunemente chiamata “reazione di click” è stata utilizzata per la funzionalizzazione del composto [5-(trimetilsilil)etinil]-1-metilimidazolo con un anello 1,2,3-triazolo. Utilizzando differenti agenti metilanti è possibile metilare solamente l’azoto dell’anello imidazolico (precursore del legante, i) o entrambi gli anelli imidazolico e triazolico (precursori dei leganti, l e m). Partendo dai precursori dei leganti, l e m, sono stati ottenuti complessi di argento(I) con rapporto Ag:L 1:1 (L = dicarbene N-eterociclico), anche se con bassa purezza a causa della natura oleosa dei prodotti. Utilizzando il precursore i è stato possibile isolare il complesso di argento(I) con formula AgCl(NHC), che è stato successivamente impiegato per la sintesi dei complessi di oro(I), rame(I) e rutenio(II). L’attività citotossica in vitro di tali composti è stata valutata e risultati preliminari mostrano un’attività e selettività maggiore per il complesso di argento(I) rispetto agli altri complessi metallici studiati. iii) complessi metallici con leganti eteroditopici basati su unità imidazol-2-ilideniche e triazol-5-ilideniche legate tra loro mediante ponte propilenico. Precursori dei leganti eteroditopici sono stati sintetizzati mediante reazione di click CuAAC, seguita da metilazione e scambio di anione. Una nuova serie di complessi di oro(I), con formula generale [Au2L2](PF6)2, è stata ottenuta mediante reazione di transmetallazione dell’unità dicarbenica N-eterociclica a partire dal complesso di argento(I) preformato. La medesima via sintetica è stata utilizzata per la sintesi di un complesso di palladio(II) che mostra la chelazione di due unità dicarbeniche allo stesso centro metallico. A causa della presenza di due diverse unità carbeniche (imidazol-2-ilidene e triazol-5- ilidene) è possibile ottenere una miscela di isomeri la cui composizione è stata analizzata mediante spettri NMR e tecniche di massa. iv) leganti bis(benzossazolici) e tentativi di sintesi dei corrispondenti complessi con metalli di transizione. Precursori dei leganti con anello benzossazolico sono stati sintetizzati a partire dalla relativa diammina. Queste molecole organiche sono state utilizzate come precursori dei leganti per la sintesi di diversi complessi con metalli di transizione. Sfortunatamente, nonostante le differenti condizioni di reazione utilizzate (agente deprotonante, solvente, temperatura, tempo…), i risultati ottenuti non sono soddisfacenti, probabilmente a causa dell’instabilità intrinseca dei precursori e/o dei relativi carbeni.

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17

Monticelli, Marco. „Novel di(N-heterocyclic carbene) ligands and related transition metal complexes“. Thesis, Strasbourg, 2017. http://www.theses.fr/2017STRAE051.

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Le travail de thèse, en co-tutelle entre l'Université de Padoue et l'Université de Strasbourg, se concentre sur la chimie des carbènes bis-(N-hétérocycliques) et peut être divisé en quatre familles de ligands qui constituent les quatre chapitres du manuscript : i) complexes métalliques de Cu(I), Ag(I), Au(I), Ir(III) et Ru(II) avec des ligands di(carbène N-hétérocyclique) portant un pont phénylène rigide entre les unités carbèniques; ii) complexes métalliques de Cu(I), Ag(I), Au(I) et Ru(II) combinant un ligand NHC fonctionnalisé avec un triazole dans la position 5 du squelette; iii) complexes métalliques d’Ag(I), Au(I) et Pd(II) avec des ligands hétéroditopiques à base d'un imidazol-2-ylidène et d’un 1,2,3-triazol-5-ylidène reliés par un pont propylène; iv) proligands bis (benzoxazoles) et les tentatives de complexation sur des métaux de transition
The PhD, a collaboration between the University of Padova and the University of Strasbourg, is focused on the chemistry of di(N-heterocyclic carbene) ligands and can be divided in four families of ligands that constitute the four chapters: i) metal complexes (Cu(I), Ag(I), Au(I), Ir(III), Ru(II)) with di(N-heterocyclic carbene) ligands bearing a rigid phenylene bridge between the carbene units; ii) metal complexes (Cu(I), Ag(I), Au(I), Ru(II)) combining an imidazole-based NHC ligand functionalized with a triazole in the 5 position of the backbone; iii) metal complexes (Ag(I), Au(I), Pd(II)) with heteroditopic ligands based on imidazol-2-ylidene and 1,2,3-triazol-5-ylidene moieties connected with a propylene bridge; iv) bis(benzoxazolium) proligands and attempted synthesis of related transition metal complex

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18

Paesch, Alexander Noel. „Syntheses of Novel Side-Arm Functionalized N-Heterocyclic Silylene Transition Metal Complexes“. Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2019. http://hdl.handle.net/21.11130/00-1735-0000-0003-C1AA-3.

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19

Halepoto, Dost Muhammad. „Syntheses and structures of some novel chromium(II), vanadium(II) and vanadium(III) complexes“. Thesis, University of Surrey, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.375971.

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20

Sakarya, Nurguen. „Novel triphosphole and selenadiphosphole coordination complexes“. Thesis, University of Sussex, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.362275.

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21

Clarke, Catherine Ann. „The synthesis and characterisation of transition metal complexes of some novel chiral multidentate ligands“. Thesis, Heriot-Watt University, 1998. http://hdl.handle.net/10399/1111.

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22

Melchionna, Michele. „Synthesis and study of novel zwitterionic transition metal complexes and their application as olefin polymerisation catalysts“. Thesis, University of Edinburgh, 2007. http://hdl.handle.net/1842/6571.

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The synthesis, characterization and coordination chemistry of novel zwitterionic late transition metal complexes has been carried out, and an investigation of their ability to act as olefin polymerisation catalysts has been conducted. These systems are based on 6- aminofulvene-2-aldiminate ligands (R2AFA¯) which are capable of binding metal centres via two nitrogen donors, delocalising the negative charge into their cyclopentadienyl moiety, thus resulting in the formation of neutral zwitterionic complexes. Preparation and characterisation of mono- and di-substituted complexes such as Ph2AFACuPPh3, (Ph2AFA)2Zn, (Ph2AFA)2Co, (Ph2AFA)2Ni and (Ph2AFA)2Pd have revealed that this type of ligand has enough flexibility to distort upon coordination to the metal depending on geometrical or steric restrictions. As a result, when the ligand coordination involves narrow binding angle of the metal chelate, as it happens in the square-planar species, a severe loss of planarity of the ligand framework is observed, in contrast with the tetrahedral structures where such binding angles are wider. Although the coordination of the ligand primarily occurs through the nitrogen donors, once they have been occupied by the metal centre, it is possible to exploit the aromatic Cp ring for coordination to a Cp*Ru+ unit. In this way, the synthesis and characterisation of two- and tri-metallic complexes [(Cp*Ru)(Ph’2AFA)Pd(η3-C3H5)][BF4] (where Ph’= 2,4,6-trimethylphenyl) and [(Cp*Ru)2(Ph2AFA)2Pd][BF4]2 has been achieved, featuring the R2AFA¯ molecule acting as an ambidentate ligand, binding the palladium atom in a diimine fashion and the ruthenium centres by means of the C5 ring. The synthesis of the complex Cp*RuPh2AFA where the two N atoms are vacant was also achieved and it was found that this compound acts as a proton sponge in the presence of protic solvents. In an effort to prepare AFA-metal complexes which could be of potential use in olefin polymerisation catalysis, two novel species, [(Ph2AFA)Pd(Me)PPh3] and [(Ph’2AFA)Pd(C3H5)] (where Ph’= 2,4,6-trimethylphenyl) have been synthesised and characterised, and polymerisation tests with ethylene have been carried out. Some preliminary screening of other molecules as monomers for polymerisation catalysis has also been conducted.

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23

Chun, Sung-Ho. „Studies on the reversible interconversions of transition metal cluster species on a hydroxylated magnesia surface and the synthesis of novel transition metal aluminum complexes /“. The Ohio State University, 1996. http://rave.ohiolink.edu/etdc/view?acc_num=osu148794150429355.

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24

Patino, Midori Amano. „Topochemical manipulation of some complex transition metal oxides“. Thesis, University of Oxford, 2016. https://ora.ox.ac.uk/objects/uuid:e312bf34-98d5-4818-bb50-fd8772688a1d.

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This thesis is comprised of three parts. The first part concerns the investigation of the topochemical reduction of LaSrNiRuO₆ in order to prepare LaSrNiRuO₄ via anion deintercalation. The second part discusses the oxide-for-hydride anion exchanges performed in SrV_1-xTi_xO₃, and the resulting SrV_1-xTi_xO_2-yH_1+y reduction products. Finally, the results from redox-neutral topochemical cation exchange reactions conducted in the three-dimensional perovskite structure of NaTaO₃ are presented along with the characterisation of a novel product of composition Ni_0.5TaO₃. The topochemical reduction of LaSrNiRuO₆ using CaH2 was carried out to produce a novel extended oxide phase with composition LaSrNiRuO₄. This phase is composed of sheets of apex-linked Ni¹⁺O₄ and Ru²⁺O₄ squares in a checkerboard ordered arrangement. To the best of our knowledge, this material is the first example of a B-cation ordered infinite-layer oxide phase. The low oxidation states of the transition-metal cations are confirmed by DFT calculations from which a spin moment S = ½ is determined for the nickel while the ruthenium centres adopt an intermediate-spin S = 1 configuration. LaSrNiRuO4 behaves paramagnetically at room temperature. However, upon cooling (T < 250 K) a phase transition is observed in which the nickel spins interact ferromagnetically, while the ruthenium cations appear to undergo a change in spin configuration to a diamagnetic spin state. A possible explanation is given for this observation based on an ordered arrangement of local Jahn-Teller distortions. While investigating the preparation of LaSrNiRuO₄, it was observed that different samples of the LaSrNiRuO₆ starting materials exhibited markedly different reactivity. The observed differing reactivity is inconsistent with the crystal structure and composition of the LaSrNiRuO₆ samples, from which all the materials are identical. Careful investigation of the X-ray diffraction data collected from the LaSrNiRuO6 materials revealed that the reactivity of the samples is a consequence of the microstructure. By quenching or slow-cooling the materials during their synthesis, the size of the crystalline domains formed is affected and this in turn is observed to define the extent to which the topochemical deintercalation of oxide anions takes place. A mechanism to explain this effect is presented in which the greater 'plasticity' of small crystalline domains helps to limit the influence of lattice strain during the reaction. Similar with the observations for the LaSrNiRuO₆ phases, it was found that the reactivity of SrV_0.95Ti_0.05O₃ samples towards topochemical oxide-for-hydride exchange is also determined by the characteristics of the starting materials. The cooling rate can lead to phase segregation in SrV_0.95Ti_0.05O₃ samples which in turn affects the reduction behaviour. A modification of the energy profile for the oxide-for-hydride exchange in SrV_1-xTi_xO₃ phases is proposed on the basis of the electronic configuration that the transition-metal cations adopt upon reduction (d²,V³⁺ and d¹,Ti³⁺). Finally, topochemical exchange reactions can also be carried out between cations in complex transition metal oxides when the mobility of the species to be exchanged is sufficiently greater with respect to the host lattice. The preparation of Ni_0.5TaO₃ from exchange of Na⁺ by Ni²⁺ in NaTaO3 represents a synthetic approach not yet widely explored in the long-standing challenge that the preparation of magnetoelectric multiferroic materials represents. The topochemical reactions studied in this work highlight the possibility of directing and modifying the product phases, by tuning features of the reagents. This is in contrast with the limited control available in thermodynamic processes.

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25

Kruger, John Scott. „Synthesis and characterization of several novel aluminum and gallium phosphates templated by cobalt complexes“. Thesis, Georgia Institute of Technology, 1999. http://hdl.handle.net/1853/30553.

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26

Swarts, Andrew John. „Novel transition metal complexes based on N,N and N,P ligands as catalysts for ethylene transformation reactions“. Thesis, Stellenbosch : Stellenbosch University, 2014. http://hdl.handle.net/10019.1/86330.

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27

Ray, Mausumi. „Theoretical Studies on Transition Metal Complexes of Silicon Species: Their Novel Bonding Natures, Electronic Structures, and Fluxional Behavior“. 京都大学 (Kyoto University), 2009. http://hdl.handle.net/2433/84825.

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28

Alam, Md Mahbubul <1976&gt. „Synthesis and characterization of novel ligands and application of their transition metal complexes as catalysts or anticancer agents“. Doctoral thesis, Università Ca' Foscari Venezia, 2015. http://hdl.handle.net/10579/8353.

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In this Thesis work, we report an innovative approach for the synthesis of 2-bromoacrylic acid and its ester derivatives that are the key intermediates in the synthesis of chiral aryloxypropionic acid an important class of herbicides. The synthesis of the bromo substitued acrylics was carried out via carbonylation of (trimethylsilyl)acetylene using as catalytic system Pd(OCOCH3)2 in combination with CH3SO3H and 2-(6-methyl)(diphenylphosphine)pyridine. When the reaction is carried out in methanol, methyl 2-(trimethylsilyl)acrylate was obtained in good yields with a branched/linear ratio 95/5. On the other hand, hydroxycarbonylation reactions give 2-(trimethylsilyl)acrylic acid with lower conversions and selectivities (ca. 53%, and 93/7 respectively). The effects of phosphine/palladium, acid/palladium, reaction time, temperature, and CO pressure on the substrate conversion and selectivity towards branched isomer have been investigated. Methyl 2,3-dibromo-2-(trimethylsilyl)propanoate is easily prepared by reaction of methyl 2-(trimethylsilyl)acrylate with bromine in dry dichloromethane. Then bromodesylilation of 2-(trimethylsilyl)acrylate in the presence of an excess of base gives 2-bromoacrylic acid in good yield (ca. 90%). A series of triazole ligands were synthesized by the CuAAC reaction. They were employed as chelating ligands to prepare Ru(II), Pd(II), and Co(II) complexes. Ligands and metal complexes have been characterized by analytical data, ESI-MS and 1H and 13C NMR spectroscopy. The water soluble sodium 2-(1-((pyridin-2-yl)methyl)-1H-1,2,3-triazol-4-yl)ethyl sulfate ligand has been employed as ligand in biphasic water/organic solvent catalysis. A preformed ruthenium complex and an iridium system containing this water soluble pyridyl-triazolyl ligand were successfully employed in water/toluene biphasic catalytic hydrogenation of C=C and C=O double bonds. The hydrogenation of styrene, 2-cyclohexene-1-one, m-diisopropenylbenzene, and cinnamaldehyde has been investigated. The water soluble 2-(1-(2-(methylthio)ethyl)-1H-1,2,3-triazol-4-yl)ethanol ligand in combination with [RhCl(COD)]2 gives a system displaying good activity in olefin hydroformylation. The above water soluble [RuCl(η6-p-cymene)(sulphated ligand)] complex has been tested in vitro against several human cancer cell lines (A375, A431, BxPC3, A549 and HCT-15.) derived from solid tumors by the MTT test. Preliminary results indicate that the ruthenium complex is less cytotoxic than cisplatin but has a potential as antimetastatic agent.

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29

Thornley, Paul Andrew. „The Synthesis and Characterisation of a Novel Polyamine-Terpyridine Ligand and Related Complexes“. Thesis, University of Canterbury. Chemistry, 2009. http://hdl.handle.net/10092/2583.

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This project was aimed at synthesising, characterising and examining the properties of the novel polyamine ligand 4’-{2’”-(12-Amino-2,6,9-triazadodecyl)-phenyl}-2,2’:6’,2”-terpyridine and its related complexes. The ligand would be based around the 4’-(o-toluyl)-2,2’:6’,2”-terpyridine framework and have potential applications in analytical chemistry. The 4’-(o-toluyl)-2,2’:6’,2”-terpyridine framework would have a tail attached on the functionalised o-toluyl methyl group. The ortho toluyl functionality was chosen so that the donor atom containing tail would be directed back towards the coordination site. This would make it easier for the tail to interact with a central metal ion. There is potential to be able to change the number and type of donor atom in the tail so that the ligand may be metal ion selective. As the tail would contain donor atoms, the denticity of the ligand would be increased making it more applicable for complexometric titrations. The 2,2’:6’,2” terpyridines exhibit strong colours when coordinated to selective metal ions and so would have potential applications in colorimetry also. The ligand was successfully synthesised and characterised. In a multi-step process, the 4’-(o-toluyl)-2,2’:6’,2”-terpyridine underwent radical bromination before the tail was attached. The tail used in this research was N,N'-bis (3-aminopropyl)ethane-1,2-diamine (3,2,3-tet). The secondary amines in this polyamine tail were protected before addition to the brominated 4’-(o-toluyl)-2,2’:6’,2”-terpyridine to ensure terminal addition. After the tail addition, a two step separation process purified a sample of 4’-{2’”-(12-Amino-2,6,9-triazadodecyl)-phenyl}-2,2’:6’,2”-terpyridine for analysis. Due to the late stage in this research where a successful separation technique was found, little work was done on examining the properties of this ligand and its complexes.

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30

Berro, Patrick. „Exploring Photocatalytic and Electrocatalytic Reduction of CO2 with Re(I) and Zn(II) Complexes and Attempts to Employ a Novel Carbene Ligand to this Endeavor“. Thesis, Université d'Ottawa / University of Ottawa, 2021. http://hdl.handle.net/10393/41625.

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With the blend of addressing issues of sustainable energy with the environmental worries regarding emission of greenhouse gases, there is a motivation to target the efficient chemical reduction of CO2. Re(I) integrated photosensitizers and catalysts, synthesized from commercially available ligands, are introduced with the selective CO2 reduction of formic acid, making for a unique class of Re(I) catalysts typically selective for CO as a reduction product. Furthermore, synthesized Zn(II) phosphino aminopyridine complexes are structurally and computationally characterized as well as observed to function as unprecedented electrocatalysts for the reduction of CO2 to formic acid and CO. Lastly, with the importance and popularity of N-heterocyclic carbenes (NHCs) as a class of ligands in the field of organometallic catalysis, six-membered perimidine based carbenes are further explored. Synthesis of a chelating pyridyl-perimidine NHC in addition to potential transition metal catalysts are also attempted.

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31

Shimizu, Daisuke. „Synthesis of novel polythioether ligands bearing bulky substituents and their applications to the synthesis of the transition metal complexes“. 京都大学 (Kyoto University), 2006. http://hdl.handle.net/2433/144211.

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32

Paesch, Alexander Noel [Verfasser], Dietmar [Akademischer Betreuer] Stalke, Dietmar [Gutachter] Stalke und Franc [Gutachter] Meyer. „Syntheses of Novel Side-Arm Functionalized N-Heterocyclic Silylene Transition Metal Complexes / Alexander Noel Paesch ; Gutachter: Dietmar Stalke, Franc Meyer ; Betreuer: Dietmar Stalke“. Göttingen : Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2019. http://d-nb.info/1194235131/34.

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33

Macindoe, L. A. „Preparation and charecterisation of novel complexes of various mono- and di-acetylenes with transition metals“. Thesis, Edinburgh Napier University, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.380717.

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34

Diehl, Marcel [Verfasser]. „Polynuclear dioxolene complexes with redox-active transition metals – novel synthesis routes, characterization and capabilities / Marcel Diehl“. Mainz : Universitätsbibliothek Mainz, 2016. http://d-nb.info/1105421090/34.

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35

Haas, Isabelle [Verfasser], und Rhett [Akademischer Betreuer] Kempe. „Novel N-Ligand Stabilized Transition Metal Complexes of the Group IV Triad as Efficient Catalysts for Polymerization and Oligomerization / Isabelle Haas. Betreuer: Rhett Kempe“. Bayreuth : Universität Bayreuth, 2013. http://d-nb.info/106000948X/34.

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36

Gurram, Venkata Narayana [Verfasser], und Michael R. [Akademischer Betreuer] Buchmeiser. „Novel early and late transition metal complexes for the synthesis of functional vinyl-insertion and metathesis polymerization-derived block-copolymers / Venkata Narayana Gurram. Betreuer: Michael R. Buchmeiser“. Stuttgart : Universitätsbibliothek der Universität Stuttgart, 2012. http://d-nb.info/1021687448/34.

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37

Lidster, Jon. „Design and synthesis of new metallo-organic complexes and their evaluation as anti-cancer agents : synthesis, characterisation and biological evaluation of novel, late first row transition metal Schiff base complexes, as anti-cancer metallopharmaceuticals“. Thesis, University of Bradford, 2011. http://hdl.handle.net/10454/5679.

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This work is concerned with the design and synthesis of the cheap, late first row transition metal complexes of Schiff base ligand systems. The prepared complexes readily afford systematic variation in order to probe potency and understand the role of metal, chelating ligands and anionic ligands when carrying out their cytotoxic effect. This study has lead to a better understanding of the action of these classes of complex and will be used to direct the design of new anti-cancer metallopharmaceuticals going forward. This thesis details the synthesis of a library of Schiff base macroacyclic ligands and their novel late first row transition metal complexes with varying anionic counterparts. The creation of a library with several degrees of variability provides a wide array of parameters to afford subtle variation in structure and chemistry e.g. denticity, co-ordination mode, chelate hole size, metal centred redox potentials, hydrolysis rates, co-ordinative saturation, lipophilicity, solubility and more. Complexation of the ligands was carried out by the free ligand and a novel macroacyclic metal template approach using the cheap late first row transition metal salts of Cobalt (II), Nickel (II), Copper (II) and Zinc (II) plus one Ru (III) complex. Structural studies of the 80 generated complexes was carried out by vibrational spectroscopy, elemental analysis, mass spectrometry, magnetic susceptibility and NMR. Single crystal X-ray structures have been determined with 20 reported in this thesis. All ligands act as tridentate ligands in all except one case to form monomeric distorted trigonal-bipyramidal, square-pyramidal or octahedral structures. In the case of zinc nitrate, the ligand L2PhMe acts as a tetradentate ligand to give a distorted octahedral structure. Paramagnetic NMR and solution magnetic susceptibility of paramagnetic complexes was achieved by the Evans NMR method and analysis of the solution NMR showed that L2R and L3R ligands display 2-fold symmetry and are likely either tetradentate in solution or a fast exchange between imine N-donar sites is occurring even down to -65°C. The majority of the resulting complexes of L1R were screened against a panel of three cancer cell lines. Several categories of complex were able to afford structure activity relationships. It was discovered that the ligand is indeed essential for activity of the metal salts against the panel of cell lines and it was largely discovered that the variation in 'tail group' and anionic coordinating ligands played little role in providing a dramatic variation in activity of the metal salt. In general all L1R complexes displayed moderate cytotoxicity showing a trend in activity with respect to the metal in the order RuIII≈CoII>CuII≈ZnII>NiII, over a 6 day exposure to the three cell panel RuIII was shown to be the most potent metal of the L1R series providing IC50 values of 4.6 (0.7) and 7.5 (1.2) μM against the DLD-1 and H460 cell lines respectively, which is Ca. 4.6 and 15 times less potent than cisplatin to the same cell panel respectively. RuIII was also discovered to be the only metal to provide an IC50 value from a 1 hour exposure to the DLD-1 cell panel. The value of 20.4 (3.5) μM is a moderate figure but again Ca. 10 fold less potent than cisplatin for the same test. The L2R and L3R complexes could not be screened by the same comprehension due to their low solubilities. However the lone screen that was possible from the very sparingly soluble complex [CuCl2(L3Bui)] gave the most exciting result and most potent complex of this thesis. After a 6 day exposure, [CuCl2(L3Bui)] gave IC50 values of 4.3 (0.1) and 2.9 (0.1) μM against the DLD-1 and H460 cell lines respectively. These values are merely 4 and 6 fold more than Cisplatin to the same cell lines respectively and demonstrates the potential of this class of complex as cytostatic agents. Further studies utilising a semi-quantitative DNA damaging assay, demonstrated that all first row complexes can damage DNA when in the presence of hydrogen peroxide, with the exception of ZnII complexes. CoII appeared to afford the greatest DNA damage with the most intsense bands for double strand breaks and the CuII complex of the ligand L3Bui also demonstrated a greater DNA damage as opposed to its L1Bui analogue.

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38

Barron, Andrew Ross. „Transition metal aluminohydride complexes“. Thesis, Imperial College London, 1986. http://hdl.handle.net/10044/1/37935.

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39

Jasim, Naseralla. „Transition metal bifluoride complexes“. Thesis, University of York, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.323538.

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40

Zard, P. W. „Transition metal complexes with pyrimidinethiones“. Thesis, Imperial College London, 1988. http://hdl.handle.net/10044/1/47322.

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41

Johnson, Donald Martin. „Cyanoscorpionates and Transition Metal Complexes“. Digital Commons @ East Tennessee State University, 2010. https://dc.etsu.edu/etd/1725.

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The new dihydrobis(4-cyano-3-tert-butylpyrazolylborate) ligand has been synthesized. Isolated crystals of the thallium complex were collected and structurally characterized by X-ray diffraction. Transition metal complexes of the ligand are currently under investigation.

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42

Michie, Charles. „Novel transition metal oxynitrides“. Thesis, University of Oxford, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.289404.

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43

Börger, Carsten, Olga Kataeva und Hans-Joachim Knölker. „Novel approach to biscarbazole alkaloids via Ullmann coupling – synthesis of murrastifoline-A and bismurrayafoline-A“. Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2014. http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-139195.

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Unprecedented Ullmann couplings of murrayafoline-A with either 6-bromo- or 4-bromocarbazole derivatives provide highly efficient synthetic routes to the biscarbazole alkaloids murrastifoline-A (6 steps, 66% overall yield) and bismurrayafoline-A (6 steps, 28% overall yield)
Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich

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44

Holder, Alan John. „Studies on transition metal macrocyclic complexes“. Thesis, University of Edinburgh, 1987. http://hdl.handle.net/1842/10961.

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45

Cheung, Wai Man. „Transition metal complexes with dichalcogenoimidodiphosphinate ligands /“. View abstract or full-text, 2007. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202007%20CHEUNG.

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46

Redfern, C. M. „Electronic structure of transition metal complexes“. Thesis, University of Oxford, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.235094.

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47

Mobbs, B. E. „Arene transition metal complexes in synthesis“. Thesis, University of Oxford, 1985. http://ora.ox.ac.uk/objects/uuid:4c7030d4-297e-4af8-a622-d5b4963fc0a3.

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This thesis deals with the applications of organopalladium and organochromium chemistry to the functionalisation of the benzopyran ring system, at a variety of oxidation levels. Section I demonstrates the functionalisation of 3-, 6-, and 8-bromochromones via palladium (0) insertion into the C-Br bond. The resultant arylpalladium species are shown to undergo addition to the least substituted end of a variety of olefins including methyl acrylate, acrylonitrile and styrene. Subsequent palladium-hydride elimination leads to overall palladium catalysed vinylation of the chromone and the synthesis of a number of novel compounds. Vinylation occurs regiospecifically at the site of chromone bromination and is shown to allow clean substituent introduction into each of the three sites. The palladium catalysed reaction of 3,6-dibromo-chromone with methyl acrylate leads to vinylation at both the C3 and C6 positions. Carbonylation of the 6-bromochromone in ethanol or butanol leads to the 6-ethyl or 6-butyl esters respectively. The palladium catalysed vinylation of the 6-bromochromone with ethyl vinyl ether leads to a mixture of products from addition of the chromone to either end of the olefin. With p-bromophenol or p-bromo-N,N-dimethylaniline the reaction gives exclusively the acetylated product arising from addition to the more substituted end of the olefin. This change in orientation is rationalised by considering the polarisation of the olefin and the arylpalladium species. Section II demonstrates the functionalisation of chroman and 4-chromanol via coordination to the Cr(CO)₃ moiety. (η⁶-Chroman)Cr(CO)₃ is synthesised and is shown to undergo regiospecific ring deprotonation at C8 under kinetic conditions or regiospecific benzylic deprotonation at C4 under thermodynamic conditions. The resultant anions are quenched with alkyl halides, aldehydes, Eschenmoser's salt and methyl disulphide resulting in selective functionalisation of either site. No mixed products are observed. The uncomplexed arene is shown to be totally unreactive under identical conditions. (η⁶-4-Chromanol)Cr(CO)₃ is synthesised and is shown to undergo regiospecific C8 ring deprotonation by comparison with authentic samples of the C5 and C8 methylated alcohols. Protection of the hydroxyl group as its methyl, t-butyldimethylsilyl or methoxymethyl ethers is found not to alter the regiochemistry of deprotonation. The 4-chromanol t-butyldimethylsilyl and tri-i-propylsilyl ethers are synthesised and coordinated to the metal unit. Cleavage of the silyl ethers is shown to proceed with loss of stereochemistry, indicating C-0 bond cleavage.

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48

Bridgewater, Brian Michael. „Sterically hindered chiral transition metal complexes“. Thesis, Durham University, 1998. http://etheses.dur.ac.uk/5022/.

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This thesis describes the synthesis, characterization and study of a series of organometallic compounds which all contain the same new ligand, l-phenyl-3-methyl-4,5,6,7-tetrahydroindenyl. The ligand forms a chiral complex once coordinated, and is relatively bulky when compared with ligands such as cyclopentadienyl or 4,5,6,7-tetrahydroindenyl.Chapter one of this thesis introduces cyclopentadienyl ligand chirality, cyclopentadienyl metal complex chirality and sterically demanding cyclopentadienyl systems. The synthesis and chemistry of tetrahydroindenes and some applications of chiral cyclopentadienyl metal complexes and their bulky analogues are also reviewed. Chapter two describes modifications to a literature preparation of the tetrahydroindenone precursor of the new tetrahydroindenyl ligand which lead to higher yields. The synthesis of the ligand itself is described, as well as the synthesis of a benzylidene-substituted hexahydroindene, which demonstrates a limitation in the flexibility of the synthetic route chosen. The synthesis, characterization and various properties of the following iron(II) compounds are discussed in chapter two; bis-l-phenyl-3-methyl- 4,5,6,7-tetrahydroindenyl iron (II), 2.3, l-phenyl-3-methyl-4,5,6,7-tetrahydroindenyl iron(II) dicarbonyl dimer, 2.4, and l-phenyl-3-methyl-4,5,6,7-tetrahydroindaiyl methyl dicarbonyl iron(II), 2.5. For all these iron complexes, the solid state molecular structures and the absolute configuration of the chiral ligand were determined using single crystal X-ray d iffraction. For 23 and 2.4, three isomers are possible, two enantiomers that are collectively termed the rac-isomer and a third isomer, the meso- isomer. Cyclic voltammetric studies on 2.3 indicate that it has a reversible one electron oxidation at 0.187 V (with respect to a non-aqueous Ag/AgCl standard electrode). The difference between this and the reversible one electron oxidation for (η-C(_5)H(_5))(_2)Fe (with respect to the same standard) is -0.314 V, therefore 2.3 is shown to be much more easily oxidized than (η-C(_5)H(_5))(_2)Fe. The solution-state infi-a-red spectrum of 2.4 is explained, with reference to a literature analysis of the unsubstituted analogue [CpFe(CO)(_2)](_2). The steric forces present in the various molecular environments are discussed in connection with the degree of phenyl-ring tilt relative to the cyclopentadienyl mean plane and the deviation of the other cyclopentadimyl substituents away from the metal centre. Subsequent reactions of compounds 2.4 and 2.5 are described. Attempts to make linked analogues of the new ligand are summarized in chapter two. In chapter three, two Zr(rV) compounds are prepared, bis (l-phenyl-3-methyl-4,5,6,7-tetrahydroindenyi) zirconium(fV) dichloride, 3.1, and bis (l-phenyl-3-methyl-4,5,6,7-tetrahydroindenyl) dimethyl zirconium(TV), 3.2. Upon crystallization, rac-3.1 spontaneously resolves into crystals containing only one enantiomer. The similarities and differences in the spectroscopic data for the iron(n) compounds of chapter two and the zirconium(IV) compounds of chapter three are discussed and possible explanations offered . The solid state molecular structures of 3.1 and 3.2 were determined by single crystal X-ray diffraction. Experimental details are given in chapter four, whilst the characterizing data are presented in chapter five. Details of the X-ray structure determinations are given in Appendix A.

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49

Wardell, E. M. „EXAFS studies on transition metal complexes“. Thesis, University of Manchester, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.377729.

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50

Atkins, Andrew J. „Studies on transition metal macrocyclic complexes“. Thesis, University of Edinburgh, 1993. http://hdl.handle.net/1842/11664.

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