Dissertations / Theses: 'Rhodium iii complexes'

1

Pater, Boke Chan de. "Terpyridine complexes of rhodium (I, III)." [S.l. : Amsterdam : s.n.] ; Universiteit van Amsterdam [Host], 2003. http://dare.uva.nl/document/70850.

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Goswami, Niranjan. "105Rh(III) complexes with acyclic tetrathioether ligands : potential radiotherapeutic agents /." free to MU campus, to others for purchase, 1996. http://wwwlib.umi.com/cr/mo/fullcit?p9812951.

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Karpin, George W. "Synthesis and Antimicrobial Activity of Half-Sandwich Ir(III), Rh(III), and Co(III) Complexes." Diss., Virginia Tech, 2017. http://hdl.handle.net/10919/79414.

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This dissertation describes the synthesis and antimicrobial use of a series of half-sandwich Ir(III), Rh(III), Co(III) amino acid and ethylenediamine complexes. This investigation focuses on the formulation (ηn-arene)M(L)X, (L = ethylenediamine or α-amino carboxylate), (M= Ir, Rh, Ru, Co). Arene, Ligand and metal center variations were designed to tailor antimicrobial activity specific for each organism studied (Staphylococcus aureus or Mycobacteria). Each of the D/L-amino acids formed a diasteromeric complex with chiral centers on both the metal center and amino acid ligand. The unique chirality of each center elicits different antimicrobial activity against the Mycobacteria studied. The metal center (M), arene ligand (ηn-arene), and amino acid (aa), were changed independently and studied for the antimicrobial activity. In a similar fashion, each of the complexes modified with ethylenediamine and diamine derivatives were studied for their antimicrobial activity against S.aureus. All complexes were synthesized,characterized by nuclear magnetic resonance (NMR), high-resolution mass spectroscopy (HRMS), single-crystal X-ray diffraction, and elemental analysis. During the course of this work it was found that the amino acid complexes with all metal centers were specific for antimicrobial activity against all types of Mycobacteria, while the diamine derivatives were active against different strains of S.aureus. Acitvity was measured to be as low as 2 ug/mL respectively depending on the complex used. A structure activity relationship was developed to determine what combinations of ligand, metal and arene were necessary to achieve the highest antimicrobial activity. The optimal arene R-chain length for CpR was determined to be R=hexyl for all complexes studied. The most active amino acidcomplex was determined to be that of L-phenylglycine for Mycobacteria, the cis-1,2-diaminocyclohexane complex is the most active ligand against S.aureus. Each metal center had similar activity levels. Toxicological studies were performed to test their viablity to be used in mammalian systems. The complexes with the highest activity were studied against several mammailan cell lines and revealed that mammailan cells were undergoing normal cellular processes at up to 40 times the minimal inhibitory concentration (MIC). A study of the MOA or mechanism of action revealed the ability of the amino acid complexes to affect the peptidyl transferase region on the 23s ribosomal subunit of M.smegmatis. This was accomplished by isolating resistant strains of M.smegmatis towards the most effective complex (Cp*hexyl)Ir(L-phenylglycine)-Cl. Cross drug resistance of these mutants was shown with clarithromycin. The DNA of the 23s ribosomal subunit was sequenced revealing a deletion/insertion mutation within domain V (bases 2057-2058).
Ph. D.

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4

Anderson, Margaret. "An electrochemical and kinetic investigation of some rhodium (III) complexes." Thesis, University of the West of Scotland, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.294070.

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Matharu, Daljit. "Synthesis and applications of rhodium (III) complexes for asymmetric catalysis." Thesis, University of Warwick, 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.445516.

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6

Bonnington, Kevin John. "Reactive rhodium (III) methyl complexes : kinetics, mechanisms and polymerisation catalysis." Thesis, University of Sheffield, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.419638.

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Vitorino, Susana Ricardo. "Rhodium(III) supramolecular complexes : synthesis, DNA binding and biological studies." Thesis, University of Birmingham, 2011. http://etheses.bham.ac.uk//id/eprint/2814/.

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The work described in this thesis concerns the synthesis, DNA binding and cytotoxicity studies of new Rh(III) supramolecular complexes. Chapter 1 reviews DNA molecular recognition by synthetic agents; exploring the different DNA binding modes and their importance in the anticancer properties of several metallodrugs. Special attention is given to the exciting cylinder agents, which underpin the work in this thesis and to the work with rhodium complexes and their studies with DNA and as anticancer drugs. Chapter 2 describes the synthesis, purification and characterization of Rh(III) mononuclear, dinuclear single, double and triple stranded complexes. NMR, MS, UV‐Vis, elemental analyses and in some cases X‐ray crystallography are discussed in detail. In Chapter 3, DNA binding properties of the Rh(III) complexes are explored by CD and LD spectroscopy. Gel Electrophoresis experiments are also carried out using plasmid DNA (pBR322). The dinuclear complexes are found to bind to ct‐DNA and to have more dramatic effects than the mononuclear analogues. In addition they were found to cleave plasmid DNA. Chapter 4 presents cytotoxicity studies for some of the complexes synthesized against breast and ovarian cancer cell lines. A PCR study with the Rh(III) double stranded isomers is also carried out demonstrating that these complexes are able to inhibit and block DNA transactions as represented by PCR DNA replication.

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Ballard, Beau Jurisson Silvia S. "Synthesis and evaluation of ¹⁰⁵Rhodium (III) complexes of phosphine chelate systems." Diss., Columbia, Mo. : University of Missouri--Columbia, 2008. http://hdl.handle.net/10355/6693.

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Title from PDF of title page (University of Missouri--Columbia, viewed on Feb 25, 2010). The entire thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file; a non-technical public abstract appears in the public.pdf file. Dissertation advisor: Dr. Silvia Jurisson. Vita. Includes bibliographical references.

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Akgun, Zeynep. "Synthesis and evaluation of 105Rhodium(III) complexes derived from diaminodithioether (DADTE) ligands." Diss., Columbia, Mo. : University of Missouri-Columbia, 2006. http://hdl.handle.net/10355/4340.

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Thesis (Ph. D.) University of Missouri-Columbia, 2006.
The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on July 30, 2006). Includes bibliographical references.

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Nallas, Girlie Naomi A. "Heteronuclear trimetallic polyazine complexes of iridium (III) or rhodium (III) as electrocatalysts for the reduction of CO2." Diss., Virginia Tech, 1996. http://hdl.handle.net/10919/40465.

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11

Simonato, Jean-Pierre. "Chimie de coordination de la tétraméthylchiroporphyrine avec le fer(III), le cobalt(III) et le rhodium(III) : applications à l'analyse d'énantiomères d'amines, à la complexation énantiosélective d'aminoalcools, et à la catalyse d'aziridination asymétrique." Université Joseph Fourier (Grenoble), 1999. http://www.theses.fr/1999GRE10051.

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Des complexes metalliques de la tetramethylchiroporphyrine, de symetrie et possedant des groupements meso derives du biocartol, ont ete synthetises, caracterises, et utilises dans quatre axes de recherches. _la caracterisation du complexe bis-ethanol de la tetramethylchiroporphyrine de fer(iii), en solution et en phase solide, revele que ce compose presente un etat de spin inhabituel : le spin intermediaire pur (s = 3/2). _l'insertion d'un metal diamagnetique, le cobalt(iii), coordonnant les amines au cur de la porphyrine, a permis l'analyse qualitative et quantitative de la composition de derives d'amines par resonance magnetique nucleaire du proton. Cette methode s'est averee precise, fiable, rapide et tres facile d'utilisation. _l'addition de -aminoalcools sur cette meme molecule resulte en la complexation preferentielle d'un enantiomere. Les aspects cinetiques et thermodynamiques ont ete abordes, et une explication quant a l'enantioselectivite observee est avancee sur la base de liaisons hydrogene intramoleculaires de type c-h___o. _parmi differentes complexes de la tetramethylchiroporphyrine, ceux de fer(iii) et de manganese(iii) ont donne les meilleurs resultats pour la catalyse d'aziridination asymetrique, avec des exces enantiomeriques allant jusqu'a 57% pour le styrene. Un point remarquable est l'induction asymetrique opposee de ces deux catalyseurs, chacun favorisant la formation majoritaire d'un enantiomere.

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12

Caix, Chrystelle. "Propriétés électrochimiques des complexes du type ((eta5-Me5C5)M(L)Cl)+ (M=Ir(III), Rh(III)) en solution et immobilisés dans des films de polymère : application à l'électrocatalyse." Université Joseph Fourier (Grenoble), 1996. http://www.theses.fr/1996GRE10154.

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Ce memoire est consacre a l'evaluation des possibilites offertes par les complexes de coordination de rhodium (iii) et d'iridium (iii) du type (#5-me#5c#5)m(l)x#+ en electrocatalyse. Nous nous sommes plus particulierement interesses a leur application (en phase homogene ou immobilises a la surface d'une electrode sous forme de films polypyrroliques) a l'electroreduction catalytique des protons en hydrogene moleculaire, a l'hydrogenation electrocatalytique de substrats organiques insatures, et a la reduction electrocatalytique du dioxyde de carbone. Une partie de ce travail a consiste a etudier en detail les proprietes electrochimiques des complexes chlorure d'iridium et de rhodium du type (#5-me#5c#5)m(l)cl#+ et a determiner les conditions permettant d'electrogenerer quantitativement les complexes hydrure correspondants, intermediaires proposes dans de nombreux processus catalytiques. Une etude similaire a ete conduite sur des electrodes modifiees par electropolymerisation de ces complexes, et de nouveaux materiaux moleculaires d'electrodes contenant les complexes hydrure ont ainsi ete realises. Ces complexes hydrure ont ete caracterises, en particulier pour l'iridium, par differentes methodes spectroscopiques, aussi bien en solution que sur electrodes modifiees. Enfin ces complexes et plus specialement ceux du rhodium se sont averes etre de bons catalyseurs pour l'electroreduction des protons appliquee ou non a l'hydrogenation de substrats organiques insatures et a l'electrocatalyse de la reduction du co#2 en ions formiate en milieu hydroorganique. Nous avons montre par ailleurs que, pour ces deux dernieres applications, l'immobilisation du complexe dans un film de polymere defavorise la reaction d'insertion du substrat ou du co#2 dans la liaison metal-hydrure au profit de la reduction des protons

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13

La, PenseÌe Annemarie Agnes. "Homoleptic diarsine and diphosphine complexes of iron(II), ruthenium(II) and rhodium(III) : synthesis and electrochemistry." Thesis, University of Liverpool, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.250371.

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14

Menu, Marie-Joëlle. "Nouveaux reactifs dans la chimie des complexes du rhodium, du chrome et du tungstene : les anions diazo rc(n::(2))**(-)." Toulouse 3, 1988. http://www.theses.fr/1988TOU30068.

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Synthese des complexes de rh, cr et w contenant le coordinat diazo en faisant reagir les sels de li des anions rc(n::(2))**(-) sur les complexes metalliques. On a isole: (pme::(3))::(4) rhc(n::(2))sime::(3) (pet::(3))::(3) rhc(n::(2))sime::(3), (pme::(3))::(2) rhc(n::(2))(s)p(n-ipr::(2))::(2). On a mis en evidence un complexe carbenique dimere possedant un groupe ylure, lors de la photolyse de (pet::(3))::(3) rhc(n::(2))sime::(3)

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15

Thu, Hung-yat. "Catalytic C-H bond functionalization reactions catalyzed by rhodium(III) porphyrin, palladium(II) and platinum(II) acetate complexes." View the Table of Contents & Abstract, 2006. http://sunzi.lib.hku.hk/hkuto/record/B38027872.

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16

Lee, Wei-Tsung. "Tris(guanidinato)complexes of iridium and rhodium in the oxidation states +III and +IV: synthesis, characterization, and reactivity." Diss., University of Iowa, 2011. https://ir.uiowa.edu/etd/2736.

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Mononuclear [Ir{ArNC(NR2)NAr}(C8H14)2] complexes (where R = Me or Et; Ar = Ph or 4-MeC6H4; and C8H14 = cis-cyclooctene) were synthesized from the neutral N,N-dialkyl-N′,N′′-diarylguanidines via deprotonation and transmetalation. As confirmed by single-crystal structure determination, the guanidinato(1−) ligands coordinate the low-valent d8 IrI center in an N,N′-chelating binding mode, and the C–N distances of the CN3 core suggest that these ligands function as stronger donors than related monoanionic, bidentate nitrogen-based ligands. In the reaction of the complexes with O2, new [Ir{ArNC(NR2)NAr}]3 complexes were identified among the products, suggesting a new route for their synthesis. Tris(guanidinato) complexes of IrIII, [Ir{ArNC(NR2)NAr}3] (R = Me or Et; Ar = Ph or 4-MeC6H4), were synthesized and, as revealed by electrochemical measurements, can be oxidized reversibly at unusually low potentials. These potentials are even lower than those of other IrIII complexes with very electron-rich, trianonic ligand sets as, for example, in cyclometalated tris(2-pyridylphenyl), corrolato and tris(dithiocarbamato) complexes. Chemical oxidation by [FeCp2]PF6 afforded isolable, paramagnetic IrIV compounds, [Ir{ArNC(NR2)NAr}3]PF6, which were characterized by elemental analysis, mass spectrometry, electronic absorption and EPR spectroscopy and X-ray crystallography. The reactivity of these IrIV complexes toward mild inorganic and organic reductants and substrates with O–H bonds was investigated. Similar tris(guanidinato) complexes of RhIII, [Rh{ArNC(NR2)NAr}3] (R = Me or Et; Ar = Ph, 4-MeC6H4 or 4-MeOC6H4), were synthesized. These complexes also were oxidized reversibly at low potentials, as compared to the corresponding tris(amidinato) and tris(triazenido) complexes. Chemical oxidation by [FeCp2]PF6 afforded thermally unstable, paramagnetic RhIV compounds, [Rh{ArNC(NR2)NAr}3]PF6, which were characterized by mass spectrometry and electronic absorption spectroscopy. Furthermore, two FeII complexes of tetradentate tripodal ligands, [Fe(L1)(OTf)2] and [Fe(L2)(OTf)2]; where L1 = N,N-bis(2-benzimidazolylmethyl)-N-(2-pyridylmethyl) amine and L2 = N,N-bis[(1-methylbenzimidazol-2-yl)methyl]-N-[(pyridin-2-yl)methyl] amine; were synthesized and characterized. The 1H NMR spectra for [Fe(L1)(NCMe)2](OTf)2 and [Fe(L2)(NCMe)2](OTf)2 in CD3CN solution at ambient temperature exhibit paramagnetically shifted peaks typical of high-spin FeII complexes, while variable-temperature 1H NMR spectroscopy showed that the Fe center in [Fe(L1)(NCMe)2](OTf)2 is in a spin equilibrium and that in [Fe(L2)(NCMe)2](OTf)2 in the high-spin state (at 25 °C). Highly reactive oxoiron(IV) complexes were obtained by reaction of the FeII complexes with an excess of m-CPBA at –40 °C.

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17

Morris, David. "Design and Modification of Half-Sandwich Ir(III), Rh(III), and Ru(II) Amino Acid Complexes for Application in Asymmetric Transfer Hydrogenation Reactions." Diss., Virginia Tech, 2015. http://hdl.handle.net/10919/71819.

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This dissertation describes the design and synthesis of a series of half-sandwich amino acid complexes of the form), (aa = α-amino carboxylate), and their utility as asymmetric transfer hydrogenation catalysts of ketones. Variation of the metal center, the n-ring, and the aa was used to tune these systems for specific sets of ketones. Upon reaction with homochiral]s, the ligand environment in all of these complexes is pseudotetrahedral, leading to stereogenic metal ions (SM, RM). The addition of another stereogenic center from the amino acid ligand (the carbon, RC or SC;glycine) gives rise to two pairs of diastereomeric complexes.
Ph. D.

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18

Nkabyo, Henry Ane. "A study on the reversible photo-induced isomerisation of platinum(II) and palladium(II) complexes of the N,N-dialkyl-N’-acyl(aroyl)thioureas with reversed-phase HPLC separation from related rhodium(III), ruthenium(III) and iridium(III) complexes." Thesis, Stellenbosch : Stellenbosch University, 2014. http://hdl.handle.net/10019.1/86773.

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19

Oliveira, Ione Maria Ferreira de. "Films de polypyrroles fonctionnalisés contenant des microparticules de métaux nobles ou des complexes du rhodium (III) : application de ces matériaux moléculaires d'électrode en hydrogénation électrocatalytique." Grenoble 1, 1992. http://www.theses.fr/1992GRE10075.

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Ce travail est consacré à la préparation, à la caractérisation et aux applications dans le domaine de l'hydrogénation électrocatalytique d'électrodes modifiées (em) par des films de polypyrroles fonctionnalisés. Les em par des films de polypyrroles substitues par des groupes cationiques (groupes alkylamonium ou pyridinium) et dans lesquels des microparticules d'un catalyseur hétérogène (pd(0) ou rh(0)) ont été incorporées, présentent une grande stabilité et une forte efficacité catalytique pour l'hydrogénation de substrats organiques, malgré les très faibles quantités de métaux déposées. Une étude de la structure et de la composition élémentaire du polymère a été réalisée par microscopie électroniqueà balayage et spectrométrie d'émission auger. L'étude électrochimique de complexes |rh#i#i#i(l)#2cl#2|#+, ou l est une 2,2-bipyridine substituée par des groupes pyrrole, a montré qu'il était possible de préparer par leur électropolymérisation des films de polymères stables conservant l'électroactivité et l'activité catalytique de ces complexes. L'utilisation de ces matériaux d'électrode purement moléculaires pour l'hydrogénation électrocatalytique de composés organiques est l'application d'un concept nouveau et original dans ce domaine d'électrosynthèse

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Davis, John Christopher. "Understanding the origin of 35/37Cl and 16/18O isotope effects on 195Pt and 103Rh NMR nuclear shielding in selected Pt(IV) and Rh(III) complexes : a DFT study." Thesis, Stellenbosch : Stellenbosch University, 2013. http://hdl.handle.net/10019.1/95484.

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21

Ourari, Ali. "Étude de deux réactions d'électrocatalyse : hydrogénation électrocatalytique sur des films de polymères contenant des microparticules de métaux nobles et activation de l'oxygène par des complexes Mn(III) - bases de Schiff." Université Joseph Fourier (Grenoble ; 1971-2015), 1995. http://www.theses.fr/1995GRE10171.

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Ce travail est relatif a l'etude de deux reactions d'electrocatalyse. La premiere partie concerne la mise au point de cathodes moleculaires, realisees par l'inclusion de microparticules de metaux nobles dans des films de polypyrrole fonctionnalise et a leur application en hydrogenation electrocatalytique. L'etude de l'hydrogenation de deux substrats test, le limonene et la carvone, a montre qu'il est possible d'orienter la selectivite de ces electrodes modifiees selon la nature du metal incorpore (pt, pd ou rh). Le resultat le plus significatif est que l'incorporation dans le meme film de polymere de deux metaux d'activite catalytique differente (pt + pd ou rh + pd) conduit a des cathodes dont l'efficacite et la selectivite sont largement superieures a celle des cathodes basees sur un seul metal. La deuxieme partie de ce travail est consacree a l'etude de l'activation electrochimique de l'oxygene par des complexes mn (iii) - bases de schiff. Il apparait que le complexe mn (ii) - salen substitue en 5,5 par des atomes de chlore est le catalyseur le plus stable et le plus efficace pour la reaction test d'epoxydation du cyclooctene. D'autre part, la rigidification du complexe par l'utilisation d'un pont 1,2-cyclohexylidene ou 1,2-phenylene reliant les deux motifs salicylaldehyde du ligand, a la place du groupe ethylidene ligand salen, entraine une forte diminution de l'activite catalytique des complexes correspondants. Ce systeme electrocatalytique a egalement ete applique a l'oxydation de la tetraline et de la triphenylphosphine

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22

Boudreau, Josée. "SYNTHÈSE ET RÉACTIVITÉ D’UN COMPLEXE DE RHODIUM(III) POSSÉDANT UN LIGAND AMBIPHILE PHOSPHINE-ALANE." Thesis, Université Laval, 2011. http://www.theses.ulaval.ca/2011/28809/28809.pdf.

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Boudreau, Josée. "Synthèse et réactivité d'un complexe de rhodium(iii) possédant un ligand ambiphile phosphine-alane." Doctoral thesis, Université Laval, 2011. http://hdl.handle.net/20.500.11794/23197.

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Cet ouvrage démontre le potentiel qu'ont les ligands ambiphiles pour des applications dans des systèmes d'intérêt en activation du lien C-H d'alcanes. La synthèse du complexe Cp*RhMe2(PMe2CH2AlMe2) (Cp* = r*5-C5Me5) est présentée et l'étude de sa réactivité démontre que l'incorporation d'un fragment acide de Lewis dans la sphère de coordination secondaire de l'atome de rhodium influence significativement la réactivité au niveau de ce métal de transition. Celle-ci est enrichie par la capacité du fragment acide de Lewis d'abstraire un ligand méthylé pour former le zwitterion transitoire Cp*Rh+Me(PMe2CH2ArMe3). Il a été démontré par l'expérience et par la modélisation numérique que diverses bases de Lewis peuvent se lier à l'atome d'aluminium du complexe neutre ou au métal de transition du complexe zwitterionique, et que l'équilibre entre ces modes de coordination est dicté en partie par la « dureté » de la base de Lewis. L'influence du ligand ambiphile s'est aussi manifestée lors de l'étude de la réactivité du même complexe avec différents substrats insaturés tels que l'éthylène, les alcynes terminaux et le dioxyde de carbone. La réversibilité du processus d'ionisation s'est avéré un paramètre clé de la réaction avec l'éthylène, car suite à la formation du zwitterion Cp*Rh+H(PMe2CH2Al"Me3) le retour à l'espèce neutre Cp*RhHMe(PMe2CH2AlMe2) permet d'accéder par élimination réductrice du méthane à un intermédiaire hautement réactif de Rh(I) analogue des composés de type Cp*M(PMe3) (M = Rh, lr) capables d'addition oxydante du lien C-H d'alcanes mais typiquement générés par voie photochimique. Différents facteurs semblent faire en sorte qu'aucune addition oxydante à partir de cet intermédiaire n'a pu être observée, notamment la formation d'une interaction Rh—*»A1 qui semble stabiliser le complexe réduit. Certains paramètres qui pourraient améliorer ces résultats sont discutés. Les composés ambiphiles (PR2CH2AlMe2)2 (R = Me, Ph) interagissent en solution ou à l'état solide avec le CO2 pour former un type d'adduit préalablement formé strictement avec des « Frustrated Lewis Pairs », pourtant les composés ambiphiles présentés sont des dimères stables. L'étude de ces adduits a mené à la formation de carboxylates d'aluminium et à l'observation d'un mode d'activation inédit pour le CO2.

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Yu, Yu-Cheng, and 游育晟. "Photophysical, Electrochemical and Theoretical Studies of Cyclometalated Rhodium(III) and Iridium(III) Complexes." Thesis, 2007. http://ndltd.ncl.edu.tw/handle/92101106029709879632.

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碩士
國立成功大學
化學系碩博士班
95
The research performed in this work constitutes two major parts. The first section involves photophysical and electrochemical properties of six new cyclometalated rhodium(III) complexes. Six new cyclometalated rhodium(III) complexes of the formula [Rh(ppy)2(L)], ppy = 2-phenylpyridine and L = 2,2'-dipyridylamine (HDPA) (1), deprotonated form of 2,2'-dipyridylamine (DPA) (2), 2,2'-dipyridylketone (dpk) (3), acetyl acetone (acac) (4), 2,2'-bipyrimidine (bpym) (5), and 2,3-di-pyridin-2-yl-pyrazine (dpp) (6) have been synthesized and subjected to X-ray diffraction crystal structural, photophysical and electrochemical studies. Density functional theory (DFT) calculations have also been performed to get rationalizations of the optical orbitals and redox orbitals concerning photophysical and electrochemical data. Complexes 1 and 4 show triplet ligand centered (3LC) [pi-pi*(ppy)] phosphorescence only at 77K (460 nm for complex 1 and 462 nm for complex 4). Similar to complexes 1 and 4, the complex 2 also displays triplet ligand centered (3LC) [Pi-pi*(DPA)] phosphorescence only at 77 K (480 nm) Whereas, complexes 3, 5, and 6 exhibit triplet ligand-to-ligand charge transfer (3LLCT) [pi(ppy)-pi*(dpk, bpym, or dpp)] phosphorescence at 77K (520 nm for complex 3; 510 nm for complex 5; 506 nm for complex 6 ) and at room temperature (555 nm for complex 3 and 5; 551 nm for complex 6). All rhodium(III) complexes have similar irreversible oxidation potentials that are assigned as oxidation at ppy ligand (+1.115 V for complex 1; +1.191 V for complex 3; +0.733 V for complex 4; +1.185 V for complex 5; +1.182 V for complex 6 vs. Fc/Fc+) except the complex 2 has quasi-reversible oxidation of potential at +0.081 V vs. Fc/Fc+ which is ascribed to oxidation at DPA ligand. However, these rhodium complexes exhibit different characteristics in reduction processes: irreversible for complex 1 at -1.853 V and reversible for complexes 3, 5, and 6 at -1.308 V, -1.510 V, and -1.532 V, respectively, that are attributed to reduction at N^N ligands (HDPA, dpk, bpym, and dpp). The second part is focused on bis-cyclometalated iridium(III) complexes containing 2,2'-dipyridylamine (HDPA) or deprotonated form of 2,2'-dipyridylamine (DPA). The synthesis, X-ray crystal structure, luminescent and electrochemical properties of four new cyclometalated iridium(III) complexes, [Ir(mppz)2(HDPA)][PF6] (1), [Ir(mppz)2(DPA)] (2), [Ir(pba)2(HDPA)][PF6] (3), and [Ir(Q)2(HDPA)][PF6] (4) where mppz = 3-methy-l-phenylpyrazole, pba = 4-(2-pyridyl)benzaldehyde, Q = 2,3-diphenylquinoxaline, are reported. DFT calculations have also been performed to verify the optical orbitals and redox orbitals concerning photophysical and electrochemical data. Complex 1 shows the mixing of triplet metal-to-ligand charge-transfer and triplet ligand-to-ligand charge-transfer (3MLLCT) [d��vmppz2Ir�w→��*(HPDA)] phosphorescence only at 77K (432 nm). Complex 2 displays triplet ligand centered (3LC) [pi-pi*(DPA)] phosphorescence both at 77 K (480 nm) and 298 K (499 nm). Whereas, complexes 3 and 4 exhibit mixing of triplet ligand-centered and triplet metal-to-ligand charge transfer (3LC/3MLCT) [dpi(Ir)-pi*(pba or Q)] phosphorescence at 77K (525 nm for complex 3; 624 nm for complex 4) and 298K (533 nm for complex 3; 625 nm for complex 4). All iridium(III) complexes have similar reversible or quasi-reversible oxidation potentials that are assigned as oxidation at d�� orbitals (+0.904 V for complex 1; +1.060 V for complex 3; +1.034 V for complex 4 vs. Fc/Fc+) except complex 2 has reversible oxidation of potential at +0.100 V vs. Fc/Fc+ which is ascribed to oxidation at DPA ligand. However, these iridium(III) complexes exhibit different characteristics in reduction processes: irreversible for complexes 1 and 3 at -1.923 V and -1.759 V and reversible for complex 4 at -1.410 V, -1.645 V, and -1.888 V, that are attributed to reduction at HDPA and Q, respectively. No reductive wave was seen for complex 2 in the solvent window.

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25

Tseng, Mei-Ching, and 曾梅菁. "Synthesis, structure, photophysical and electrochemical studies of rhodium(III) and iridium(III) complexes." Thesis, 2006. http://ndltd.ncl.edu.tw/handle/49494277653095504801.

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博士
國立成功大學
化學系碩博士班
94
The research performed in this works constitutes three major parts. The synthesis, X-ray crystal structure, luminescence and electrochemical properties of four bis-cyclometalated heteroleptic Ir(III) complexes, [Ir(ppy)2(HDPA)](PF6) (1), [Ir(ppy)2(DPA)] (2), [Ir(ppy)2(dpk)](PF6) (3), and [Ir(ppy)2(pik)](PF6) (4) (where ppy = 2-phenylpyridine, HDPA = 2,2'-dipyridylamine, DPA = the deprotonated form of 2,2'-dipyridylamine, dpk = di-2-pyridyl ketone, and pik = 2-pyridyl N-methyl-2-imidazolyl ketone ) are reported in the first part. Each complex exhibits strong absorption in the UV region, due to spin-allowed π-π* transitions, and moderately intense bands in the visible region, due to spin-allowed 1MLCT transitions. In addition, weaker absorption bands and tailing at lower energy are corresponding to spin-forbidden 3MLCT transitions. The excitation polarization spectrum obtained for each complex indicates that emission chromophore behaves as linear oscillator. The emission polarization spectra of each complex, excited by 313 and 365 nm, exhibit flat with a vanished slope indicating a band of singly emission rather than multiple ones. Both at room temperature and 77K, [Ir(ppy)2(N^N)](PF6) (N^N = HDPA, dpk, pik) exhibit intense blue-green emission, assigned as 3MLCT [dπ(Ir)-π*(N^N)] phosphorescence. [Ir(ppy)2(DPA)] exhibits intense room temperature luminescence both in solution and as solid films. Assignment of the emissive behavior to a 3LLCT (DPA−-to-ppy) excited state is proposed. Analysis of voltammetric data also provides evidence in support of those assignments. 　　The X-ray crystal structure of trans-[Rh(Hbzpy)(bzpy)Cl2] and the photophysical and electrochemical studies, as well as the conformer elucidations, of cis-[Rh(bzpy)(phen)Cl2] (where bzpy = 2-(2-pyridyl- carbonyl)-phenyl and phen = 1,10-phenanthroline) are contained in the second part. trans-[Rh(Hbzpy)(bzpy)Cl2] features a Rh(III) atom that is coordinated by two N, one O, one C and two trans Cl atoms in a distorted octahedral environment. The pyridyl ring of Hbzpy and the phenyl ring of bzpy are mutually stacked to [C(1)–N(1)–C(13)–C(14) = 53.84o] and upfield shift of H(C1)/H(C14) and NOE of these H-atoms were also observed in the NMR spectrum. The NMR chemical shift data of cis-[Rh(bzpy)(phen)Cl2] is consistent with the cis-α structure. The strong σ-donor ability of the metallated phenyl ring of bzpy can move the metal d*(eg) orbitals to higher energy, resulting in the dd* emission of cis β-Rh(bipy)(bzpy)Cl2 and cis α-[Rh(bzpy)(phen)Cl2] observed at higher energy than that of cis-[Rh(bipy)2Cl2]+ and cis-[Rh(phen)2Cl2]+. In other word, bzpy exhibits the higher ligand field strength compared with that of bipy or phen. 　　The last part is focused on the X-ray crystal structure of cis-[Rh(dpk)2- Cl2][Rh(dpk)Cl4], trans-[Rh(dpk)2Cl2]ClO4, and cis-[Rh(dpk)2Cl2]ClO4 as well as the photophysical studty of trans-[Rh(dpk)2Cl2]ClO4. In the quasi-octahedral cation of cis-[Rh(dpk)2Cl2][Rh(dpk)Cl4], Rh(III) is coordinated with two dpk ligands via two pairs of nitrogen atoms and with two cis chloro ligands. The torsional angles between the pyridyl and the carbonyl group is 35.6(5)o for trans-[Rh(dpk)2Cl2]ClO4; whereas the corresponding angles for cis-[Rh(dpk)2Cl2]ClO4 are 26.7(12)o and 26.1(11)o. The former dpk are evidently more distorted due to the larger steric repulsion of the trans conformation. The trans conformer is more rigid than the cis conformer. Both at room temperature and 77K, trans-[Rh(dpk)2Cl2]ClO4 exhibits red emission, assigned as 3dd* phosphorescence.

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26

Chung, George, and 張喬智. "Photophysical, Electrochemical and Density Functional Theory Studies of Cyclometalated Rhodium(III) and Iridium(III) Complexes Containing Bridge Ligands." Thesis, 2008. http://ndltd.ncl.edu.tw/handle/18857269245941695638.

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碩士
國立成功大學
化學系碩博士班
96
The research performed in this work involved two kind of bridge ligands, 2,3-bis(2-pyridiyl)-pyrazine (dpp) and 2,2'-bipyrimidine (bpym). Dinuclear cyclometalated complexes of [Ir2(ppy)4(dpp)]2+ (1), [Rh2(ppy)4(dpp)]2+ (2), [IrRh(ppy)4(dpp)]2+ (3), [Ir2(ppy)4(bpym)]2+ (5), [Rh2(ppy)4(bpym)]2+ (6), and [IrRh(ppy)4(bpym)]2+ (7) and mononuclear cyclometalated complexes of [Ir(ppy)2(dpp)]+ (4) and [Ir(ppy)2(bpym)]+ (8) were synthesized with bridge ligand. The structure of these cyclometalated complexes were identified by X-ray diffraction crystallography and spectroscopic data. The photophysical and electrochemical properties were characterized. Density functional theory (DFT) calculations were also employed to study the orbital distribution. It was found that the orbital energy of HOMO and LUMO, the electrochemical redox potential, and MLCT bands in UV-Vis absorption spectra.changed with ligands complexing to different metal. For complexes 1 and 2, the dihedral angle of bridge ligand was found to affect the reduction potential.

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27

Sitlani, Ayesha. "Sequence specific recognition and photocleavage of DNA by phenanthrenequinone diimine complexes of rhodium(III)." Thesis, 1993. https://thesis.library.caltech.edu/7388/1/Sitlani-a-1993.pdf.

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Sequence-specific recognition and photocleavage of DNA by a series of 9,10- phenanthrenequinone diimine (phi) complexes of rhodium(III) was studied. [Rh(phi)]^(3+) complexes bind to DNA via intercalation of their phi ligand and upon photoactivation promote strand scission. The DNA degradation products formed are consistent with photoreaction of [Rh(phi)]^(3+) intercalated in the major groove of DNA, via abstraction of the C3'-H atom of the deoxyribose. For the complex [Rh(phen)2phi]^(3+) and its derivatives [Rh(X)2phi]^(3+), the primary products are 5' and 3' phosphate termini and nucleic acid bases. For the complex [Rh(phi)2bpy]^(3+) and its derivatives [Rh(phi)2X]^(3+), additional products, dependent on dioxygen concentrations, are characterized as base propenoic acids and 3'-phosphoglycaldehyde termini. The partitioning between the oxygen dependent and oxygen independent pathways correlates best with how the shapes of these complexes limit access of dioxygen to the C3' deoxyribose position. The shapes of [Rh(phi)]^(3+) complexes also govern their sequence-specific DNA recognition. The more sterically bulky complexes with methyl or phenyl groups on their ancillary ligands cleave at a subset of sequences recognized by their parent molecules. The ∆ and Λ isomers of [Rh(5,5'-dimethylbpy)2phi]^(3+) cleave specifically at sites that are defined by the consensus sequences 5'-C-T-pu/py-G-3' and 5'-A-C/G-T-C/G-3', respectively. This sequence-specificity may be understood on the basis of negative steric clashes and positive van der Waals interactions between methyl groups on the metal complex and thymine methyl groups in the DNA major groove. The complex [Rh(4,4'diphenylbpy) 2phi]^(3+) recognizes the self-complementary eight base-pair sequence 5'CTCTAGAG- 3', both due to its bulky shape and its ability to cooperatively associate through non-covalent dimerization on the DNA helix. [Rh(4,4'-diphenylbpy)2phi]^(3+) is shown to inhibit sequence-specific cleavage by the restriction enzyme Xbal. It is likely that, like [Rh(phi)]^(3+) complexes, DNA binding proteins exploit shape selection to achieve high levels of sequence-specificity.

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28

Stern, Gary Avery. "Mass spectrometric and NMR studies of some [beta]-ketoenolate and monothio-[beta]-ketoenolate complexes of rhodium(III) and iridium(III)." 1991. http://hdl.handle.net/1993/18353.

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29

"1,2-rearrangements of porphyrinato rhodium (III) alkyls- mechanistic investigation." 1998. http://library.cuhk.edu.hk/record=b6073084.

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by Kin Wah Mak.
Thesis (Ph.D.)--Chinese University of Hong Kong, 1998.
Includes bibliographical references (p. 180-195).
Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Mode of access: World Wide Web.

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30

Huang, Jen-Hsing, and 黃任興. "Electrochemical studies of mixed-ligand complexesof rhodium(III) containing N,N''—dipyridylamine." Thesis, 2002. http://ndltd.ncl.edu.tw/handle/98299401685896308629.

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碩士
國立成功大學
化學系碩博士班
90
Abstract Cyclic voltametric data have been obtained for mixed-ligand complexes of rhodium(III) containing N,N'–dipyridylamine，cis-[Rh(L-L)(HDPA)Cl2]Cl、cis-Rh(L-L)(DPA)Cl2（L-L=bipy or phen）and cis-[Rh(HDPA)2Cl2]Cl in acetonitrile. For cis-[Rh(L-L)(HDPA)Cl2] Cl，between 0∼+1.80 V vs. SCE there is a reversible oxidation peak which is +1.07∼+1.08 V and reduction peak is +0.85∼+0.87 V. This is attributed to oxidation of chloride ion. There are two irreversible reduction peaks between 0∼-1.80 V vs. SCE. Each of the reductions is one-electron reduction step followed by fast elimination of a chloride which is consistant with an ECEC（E：electron transfer，C：chemical reaction）mechanism. One can therefore suggest that their redox orbitals are assigned to be metal-localized. The luminescence had been suggested as πd* for cis-Rh(L-L)(DPA)Cl2. In electrochemical studies of these complexes，there is no peak observed between 0∼+1.80 V vs. SCE and only one irreversible reduction peak observed between 0∼-1.80 V vs. SCE. This reduction is one-electron reduction step followed by elimination of a chloride，which assigns that complexes belong to πd* transition. For cis-[Rh(HDPA)2Cl2]Cl，between 0∼+1.80 V vs. SCE there is a reversible oxidation peak which is +1.08 V and reduction peak is +0.89 V. This is attributed to oxidation of chloride ion. There is one irreversible reduction peak between 0∼-1.80 V vs. SCE. This reduction peak including two reduction steps followed by fast elimination of a chloride is consistent with an ECEC reaction. Therefore，the redox orbitals are also assigned to be metal-localized.

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