Spelling suggestions: "subject:"diimines"" "subject:"enimines""
1 |
Synthesis and characterization of pyridyl/quinolyl imine ruthenium(II) and palladium (II) complexes in catalysisSwartz, Leoni Destine January 2015 (has links)
>Magister Scientiae - MSc / We report the successful syntheses of a family of tetradentate N-donor pyridyl and quinolyl-imine ligands N1,N2-bis((pyridin-2-yl)methylene)ethane-1,2-diamine (L1), N1,N3- bis(pyridin-2-ylmethylene)propane-1,3-diamine (L2), N1,N4-bis(pyridin-2-ylmethylene) butane-1,4-diamine (L3), N1,N2-bis((quinolin-2-yl)methylene)ethane-1,2-diamine (L4), N1,N3-bis(quinolin-2-ylmethylene)propane-1,3-diamine (L5) and N1,N5-bis(pyridin-2- ylmethylene)pentane-1,5-diamine (L6). All the ligands were fully characterized by FT-IR, 1H and 13C NMR, GC-MS, Elemental analysis, UV-Vis and TGA. We report for the first time the thermogravimetric analysis of N1,N2-bis((pyridin-2-yl)methylene)ethane-1,2-diamine (L1) and N1,N2-bis((quinolin-2-yl)methylene)ethane-1,2-diamine (L4). The tetradentate N-donor pyridyl and quinolyl-imine ligands were subsequently utilised to synthesise neutral mononuclear and cationic homobimetallic ruthenium(II) complexes and new bimetallic palladium(II) complexes using the appropriate metal precursors. The ruthenium(II) complexes were evaluated for the oxidative cleavage of styrene using a Sharpless biphasic solvent system (CCl4:CH3CN:H2O) and sodium periodate (NaIO4) as the cooxidant. The bimetallic palladium(II) complexes were evaluated for their catalytic activity towards the standard Heck coupling reaction. The ruthenium(II) catalysts exhibited efficient catalytic activity, yielding conversions of 69-77%. The palladium(II) catalysts showed an overall low catalytic activity of 41-49 % conversion and analysed by GC.
|
2 |
New organic chromophores for metal complexation: investigations into the synthesis and photophysics of thioindigo diimines, azaDIMEs, and their metal complexesBoice, Geneviève Nicole 30 April 2018 (has links)
The synthesis and comprehensive characterization of diamine and diimine derivatives of thioindigo are reported. X-ray crystal structures demonstrate a planar structure for the diimine derivatives and a twisted conformation for the diamines. The diamine compounds absorb in the UV (λmax 324 nm - 328 nm), and exhibit moderate fluorescence (ΦF = 0.25, 0.045). A transient triplet state is observed in laser flash photolysis (LFP) experiments, with lifetimes an order of magnitude longer than those of the triplet state of thioindigo. The diimine compounds absorb at longer wavelengths than the diamines (λmax 495 nm - 510 nm), but are still slightly blue-shifted from thioindigo. The diimines have molar extinction coefficients 17 – 70% higher than thioindigo. The diimine compounds are not emissive, and LFP studies show transient species with microsecond lifetimes. The transient absorption spectra and quenching experiments of the diimines are consistent with trans-cis isomerisation about the central double bond.
Mono- and diruthenium hexafluoroacetylacetonate (hfac) complexes of thioindigo-N,Nʹ-diphenyldiimine have been prepared. The monoruthenium complex was isolated as a racemic mixture and the diruthenium complexes were isolated as the meso (ΔΛ) and rac (ΔΔ and ΛΛ) diastereomers. Extensive structural characterization of the compounds revealed intrinsic diastereomeric differences in the X-ray crystal structures, cyclic voltammograms, and NMR spectra. Variable temperature NMR experiments demonstrated that the rac diastereomer undergoes conformational exchange with a rate constant of 8700 sec-1 at 298 K, a behavior that is not observed in the meso diastereomer. Ground state optical properties of the complexes were examined, showing that all the complexes possess metal-to-ligand charge transfer (MLCT) absorption bands in the near-infrared (λmax 689 nm – 783 nm). The compounds do not display photoluminescence in room temperature solution-phase experiments or in experiments at 77 K. Ultrafast transient absorption spectroscopy measurements revealed excited states with picosecond lifetimes. Unexpectedly, the transient absorption measurements revealed differences in the transient spectra and disparate time constants for the excited state decay of the diastereomers, which are linked to the conformational changes observed in the NMR experiments.
Investigations into the synthesis of azaDIMEs and azaDicarbazolyls are described. Examination of the Buchwald-Hartwig amination produced reaction conditions that enabled preparation of amino-diindoles. Oxidation of the amino-diindoles to azaDIMEs was complicated by concomitant oligomerization of the substrates. Substitution of the reactive positions of the amino-diindole afforded increased stability towards oxidative oligomerization. Scalable synthetic routes to azaDicarbazolyl precursors were identified and optimized, and preparation of amino and azaDicarbazolyl compounds was explored. / Graduate / 2021-04-18
|
3 |
COORDINATION AND ORGANOMETALLIC COMPLEXES OF RHODIUM, PALLADIUM, IRIDIUM, PLATINUM AND GOLDDeligonul, Nihal 23 August 2013 (has links)
No description available.
|
4 |
Des diamino-benzoquinone-diimines aux azacalixphyrines : développement de colorants émergents du proche infrarouge / From diamino-benzoquinone-diimines to azacalixphyrins : development of emerging near infrared dyesLavaud, Lucien 16 November 2018 (has links)
Les colorants organiques du proche infrarouge présentent un intérêt majeur dans différent secteurs technologiques. Les travaux présentés dans cette thèse portent sur le développement de ce type de chromophores à partir d’unités quinones possédant une conjugaison électronique particulière : les 2,5-diamino-1,4-benzoquinone-diimines (DABQDI). De nouvelles DABQDI ont pu être synthétisées et leur utilisation comme ligand a notamment permis d’obtenir des complexes absorbant du domaine visible jusqu’à celui du proche infrarouge. Ces unités DABQDI ont également pu être incorporées au sein de macrocycles, analogues de porphyrines, appelés azacalixphyrines, capables d’absorber la lumière jusqu’à 1000 nm. / Near infrared dyes play a significant role in various technological sectors. The present PhD manuscript concerns the development of such chromophores built on quinone units that have a particular electronic delocalization: the 2,5-diamino-1,4-benzoquinone-diimines (DABQDI). New DABQDI have been synthesized and their use as ligand can provide complexes absorbing from the visible to the near infrared domain. DABQDI units were also incorporated in macrocycles, analogous of porphyrins, called azacalixphyrins, able to absorb light up to 1000 nm.
|
Page generated in 0.0525 seconds