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Dissertations / Theses on the topic 'Organomanganese complexes organic synthesis'

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Published: 4 June 2021

Last updated: 15 February 2022

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1

Bruhn, Paul Robert. "Organomanganese complexes in organic synthesis." Case Western Reserve University School of Graduate Studies / OhioLINK, 1990. http://rave.ohiolink.edu/etdc/view?acc_num=case1054841697.

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2

Patel, Hasmitta. "Organochromium complexes in organic synthesis." Thesis, Heriot-Watt University, 1988. http://hdl.handle.net/10399/995.

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3

Morris, M. D. "Organoiron complexes in organic synthesis." Thesis, University of Southampton, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.370348.

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4

Rutherford, David Thomas. "Heterobimetallic complexes in organic synthesis." Thesis, Loughborough University, 2001. https://dspace.lboro.ac.uk/2134/35604.

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Heterobimetallic cobalt-molybdenum-cyclo-penta-dienyl-alkynyl-penta-carbonyl complexes have been demonstrated to act as efficient substrates for the Pauson-Khand cycloaddition under appropriate conditions. The inherent chirality present in the heterobimetallic core has been shown to efficiently promote a stereoselective variant of the Pauson-Khand reaction. The unique mode of stereoinduction in contrast to existing methodology has enabled the first stereospecific Pauson-Khand reaction to be realised in the absence of an external source of chirality. The scope of heterobimetallic alkyne complexes for more general asymmetric organic synthetic transformations has been briefly addressed. The heterobimetallic core has been shown to promote moderate to high levels of stereocontrol on addition of nucleophiles to remote centres of complexed propargylic aldehydes. In light of the potential use of heterobimetallic complexes in organic synthesis a new robust and experimentally facile route for complex generation has been developed. Employing this route heterobimetallic complexes cim be rapidly and routinely generated avoiding specialist techniques or apparatus. Chapter 1 provides a brief overview of the Pauson-Khand reaction and developments in this field. Chapter 2 highlights our work utilising hereobimetallic alkyne complexes as substrates in the Pauson-Khand reaction, their use in more general synthetic transformations and the development of a facile but robust route for their synthesis. Chapter 3 provides experimental data for our studies.

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5

Docherty, Gordon Findlay. "Iron diene complexes in organic synthesis." Thesis, University of Strathclyde, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.367031.

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6

Bromley, L. A. "Iron acyl complexes in synthesis." Thesis, University of Oxford, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.237924.

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7

Blagg, J. "Arene chromium tricarbonyl complexes in synthesis." Thesis, University of Oxford, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.376895.

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8

Ayscough, A. P. "Stereoselective synthesis using iron acyl complexes." Thesis, University of Oxford, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.234993.

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9

Law, Ga-lai. "Synthesis and photophysical studies of organic lanthanide complexes." Click to view the E-thesis via HKUTO, 2007. http://sunzi.lib.hku.hk/hkuto/record/B38308216.

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10

Law, Ga-lai, and 羅嘉麗. "Synthesis and photophysical studies of organic lanthanide complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2007. http://hub.hku.hk/bib/B38308216.

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11

Fox, Peter Anthony 1965. "Synthesis and reactivity of organotantalum complexes containing nitrogen ligation." Diss., The University of Arizona, 1996. http://hdl.handle.net/10150/290672.

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This work examines various aspects of hydrodenitrogenation catalysis. Various tetrahydroquinolinyl (THQ) and indolinyl (DHI) complexes of tantalum were synthesized including: Ta(THQ)ₓCl₅₋ₓ(x = 1 to 5), Ta(DHI) ₓCl₅₋ₓ(THF) (x = 1 and 2). In addition, THQ and DHI complexes containing aryloxide (OAr = 2,6-diisopropylphenoxide) and alkyl complexes were also synthesized: Ta(THQ)(OAr)Cl₃(OEt₂), Ta(THQ)₂(OAr)₂Cl, Ta(THQ)(OAr)R₃Cl (R = Me and Et), Ta(THQ)₂(OAr)₂R (R = Me and Et), Ta(DHI)(OAr)Cl₃(OEt₂), and Ta(DHI)₂(OAr)₂Cl. The effects of sulfur ligation versus oxygen ligation was examined by comparison of the crystal structures of Ta[η²(N,C)-2,4,6-tri-t-butylpyridinel](OAr)₂(OᵗBu) and Ta[η²(N,C)-2,4,6-tri-t-butylpyridine](OAr)₂(SᵗBu). The sulfur ligand donates less π density to the metal center, resulting in a longer Ta-C bond for the pyridine ligand. The arene complexes (η⁶C₆Me₆)Ta(OAr)(SAr')Cl and (η⁶-C₆Me₆)Ta(OAr)(SAr'')Cl were also synthesized. These arene-thiolate complexes do not appear to bind quinoline, unlike the oxygen analogs A number of Ta(η⁴-diene)(OAr)₃ complexes were synthesized (diene = butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-cyclohexadiene) and their reactivity with respect to nitriles examined. Nitriles typically insert into Ta(η⁴-isoprene)(OAr)₃ to form (ArO₃Ta(CH₂CHCMeCH₂CRN) which can then be thermally rearranged to (ArO) ₃Ta(=NCRCH₂CHCMeCH₂) (R = Me, Ph, ᵗBu). Similar reactivity is observed with butadiene and 2,3-dimethylbutadiene diene complexes. The Ta(η⁴-C₄H₆)(OAr)₃ complex is also capable of inserting two nitriles to form (ArO)₃Ta(NCRCH₂CHCHCH₂CRN), whereas Ta(η⁴-1,3-cyclohexadiene)(OAr)₃ only forms the bis-insertion product. Aspects of the formation of the above complexes with specific concentration on the tantalum-nitrogen interactions are presented.

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12

Warner, P. "Asymmetric synthesis via transition metal acyl complexes." Thesis, University of Oxford, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.355823.

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13

Palotai, Ian Michael. "Cyclohexadiene iron complexes in lycorine asymmetric synthesis." Thesis, University of East Anglia, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.328670.

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14

Lovejoy, Andrew P. "Studies and synthesis of gallium chelate complexes." Thesis, University of Kent, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.290531.

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15

Worayingyong, Attera O. "Metal complexes as catalysts for stereoselective synthesis." Thesis, University of Aberdeen, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.294145.

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Metal complexes have been used as catalysts for stereoselective syntheses in CC bond formation reactions, namely, alkyl- and allyl- additions to aldehydes. The enantiomeric alkylations involved reactions between Et₂Zn and arylaldehydes in the presence of chiral templates, e.g. zinc-, titanium- and boron-complexes of (S)-(-)-2-amino-3-(p-hydroxyphenyl)-1,1-diphenylpropanol. The reaction has been proved to be catalytic, using 3-5 mol% of the chiral ligand in the addition of Et₂Zn to p-tolualdehyde. Study of the substituent effects in arylaldehydes showed that p-tolualdehyde leads to the highest optical yield (83%ee) when a chiral Schiff base-zinc complex is formed. The in-situ produced chiral templates for the alkylations were studied by two different methods. Firstly, the alkyl metal itself; i.e. Et₂Zn, acts as the metal key atom. Secondly, other metal compounds; i.e. BH₃.THF and Ti(OPrⁱ)₄ formed chiral auxiliary complexes for the additions of Et₂Zn to arylaldehyde. The highest optical yield for 1-p-tolylpropanol [ca. 80%ee (S)] was obtained using the zinc- and boron-complexes. The chiral amino alcohol was also deposited onto silica gel to act as a heterogeneous catalyst. The asymmetric ethylations of p-tolualdehyde using the silica gel supported ligand have been tested with zinc-, titanium- and boron-complexes. Diethylzinc alone provides the best selectivity (53%ee), the values for the boron and the titanium systems are 16 and < 1%ee, respectively. On subsequent use of the solid catalyst, the optical yields fall off. Allylic additions of Bu₃SnCH₂CH=CH₂ to arylaldehydes have been examined in the presence of the chiral amino alcohol and titanium compounds. The optimum result was found to occur when TiCl₄ was reacted with the amino alcohol prior to the simultaneous addition of the reacting materials. However, the chiral allylic alcohol was obtained in low optical yield (31%ee).

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16

Hulkes, Alexander Grant. "Synthesis and reactivity of triboronate and organochalcogen complexes." Thesis, Imperial College London, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.312817.

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17

Owen, David Alan. "Aryl substituted cyclohexanienyl iron complexes in alkaloid synthesis." Thesis, University of East Anglia, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.278063.

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18

Williams, Mark. "Lanthanide alkoxide complexes for use in asymmetric synthesis." Thesis, University of Liverpool, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.264785.

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19

Waugh, Martin Philip. "Synthesis and reactions of vinyl complexes of ruthenium." Thesis, University of York, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.357201.

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20

Wong, Ka-Leung. "Synthesis, characterization, and photophysical studies of organic-lanthanide complexes." Click to view the E-thesis via HKUTO, 2006. http://sunzi.lib.hku.hk/hkuto/record/B36875351.

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21

Wong, Ka-Leung, and 黃嘉良. "Synthesis, characterization, and photophysical studies of organic-lanthanide complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2006. http://hub.hku.hk/bib/B36875351.

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22

Cook, Darren John. "The synthesis of metallathiirenes and complexes of related ligands." Thesis, Imperial College London, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.267889.

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23

Richards, Christopher John. "The synthesis and reactivity of vinylketene and vinylketenimine complexes." Thesis, University of Warwick, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.290182.

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24

Shah, Sana. "Synthesis and Characterization of Manganese Pyridazyl Complexes." TopSCHOLAR®, 2013. http://digitalcommons.wku.edu/theses/1298.

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Heterocyclic’s and their fused-ring derivatives have been of interest for their use in electronic materials due to their ease of production, synthetic versatility, and low cost compared to traditional inorganic materials like silicon. Pyridazines have been found to be useful in catalysis gas storage, polymeric sensors and biological mimetics. When a transition-metal is fused into a synthesized pyridazine, unique properties such as conductivity and optics are allowed. In this work, synthesized pyridazine complexes will be analyzed by mass spectroscopy, elemental analysis, nuclear magnetic resonance, imaging, x-ray crystallography, and infrared spectroscopy. We are interested in synthesizing organometallic pyridazines and manganese pyridazyl complex for polymer research. Off-metal synthesis and characterization of manganese pyridazyl complex required three intermediate steps. The research focuses on the synthesis and characterization of various manganese pyridazyl complexes.

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25

Meek, Graham Andrew. "The use of π-allyltricarbonyliron lactone complexes in organic synthesis." Thesis, University of Cambridge, 1995. https://www.repository.cam.ac.uk/handle/1810/271957.

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26

Fryatt, Ross. "Heterobimetallic alkyne complexes and their use in asymmetric organic synthesis." Thesis, Loughborough University, 2004. https://dspace.lboro.ac.uk/2134/34925.

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This thesis describes the use of heterobimetallic alkyne complexes in asymmetric organic synthetic pathways. Unlike previous protocols in the literature, the source of chiral control is due to the inherent chirality of the heterobimetallic core and not from an external source. A new method for the preparation of Co(CO)3MoCp(CO)2-alkyne complexes has been addressed with a view to a more rapid and cleaner preparation of these complexes, adapting previously known literature methodology. Preparation of diastereomerically-enriched alcohol complexes has also been attempted.

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27

Cini, Melchior. "Synthesis and biological evaluation of enantiopure substituted titanocene complexes." Thesis, University of Nottingham, 2015. http://eprints.nottingham.ac.uk/30485/.

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Tolerated by normal tissues, implementation of anti-cancer therapies based on titanium compounds is limited by low efficacy/selectivity, lack of understanding of their mode(s) of action and access to the most active chiral variants. This thesis reports the synthesis, characterization and biological evaluation of a novel class of chiral substituted titanocenes from novel chiral cyclopentadienyl ligands, themselves accessible from substituted pentafulvenes. After an introductory chapter, the second chapter describes the synthesis and biological evaluation of substituted (rac/meso)-mixtures of TiCl2{η- C5H4CHEt(phenyl)}2 (abbreviated CpR2TiCl2). Addition of a substituted pentafulvene to alkyl/branched-alkyl/phenyl Grignard solutions with catalytic copper catalyst resulted in the formation of novel racemic/tautomeric cyclopentadienyl ligands in yields of up to 92%. The deprotonation of the racemic substituted cyclopentadienyl ligands with n-butyllithium and subsequent transmetallation with titanium(IV) tetrachloride resulted in the formation of novel substituted titanocene complexes in yields up to 81%. The antiproliferative activities of the (rac/meso)- mixtures of titanocenes in comparison to the simple benzyl-substituted titanocene analogue, titanocene dichloride and cisplatin were then evaluated in vitro against HCT-116, MiaPaCa-2 and MDA-MB-468 carcinoma cell lines, which represented intractable cancers from three different organ sites. All chiral substituted titanocenes were micromolar active against all the studied cancer cell lines. Finally, cyclic voltammetry studies using chiral substituted titanocenes were carried which confirmed a close to optimal fit of the chiral substituted ethyl titanocene. The third chapter reports the synthesis and biological evaluation of single enantiomers of TiCl2{η-C5H4CHEt(2-MeOPh)}2 (abbreviated CpR2TiCl2), attained through unprecedented asymmetric copper-catalysed addition of ZnEt2 to the C=C bond of substituted pentafulvenes C5H4(=CHAr) (Ar = 2-MeOPh and related species). Such enantioselective reaction resulted in enantiomerically enriched (up to 93:7 e.r.) cyclopentadienyl ligands. Copper catalyst promotion with both chiral phosphoramidite ligands and a phosphate additive was vital in realizing both acceptable enantioselectivies and reaction rates. Chloride hydrolysis of the enantiopure titanocene to [CpR2Ti(OH]+ can be detected by NMR, GCMS and LCMS in vitro under near therapeutic conditions. The anti-cancer potency of (S,S)- CpR2TiCl2 was twice that of other stereoisomers, selective for cancer cells, and the kinetics of formation of the soluble hydroxy species correlate with the latter being the biologically active species. Extensive cytoplasmic vacuolization, endoplasmic reticulum (ER) swelling and activation of MAPKinase signal transduction were consistent with ligand-induced paraptosis (type III cell death), which is morphologically distinct from, and independent of, caspase-mediated apoptosis in MDA-MB-468 and HCT-116 cells.

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28

Rettie, Alan Bruce. "Use of organometallic complexes for the synthesis of condensed cyclopentenones." Thesis, Heriot-Watt University, 1991. http://hdl.handle.net/10399/1029.

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29

Marshall, Colin. "The synthesis of chiral C2-symmetric N-heterocyclic carbene complexes." Thesis, University of Aberdeen, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.248633.

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The quaternisation of 1-substituted-azoles with a, w-dihaloalkanes furnished the diazolium salts. Conversion of the salts by deprotonation in the presence of sulphur generated the corresponding dithiones. A series of propylene diimidazolium salts and thiones gave an insight into the ease of handling, hygroscopic nature and yields associated with these compound. Propylene bridged diimidazol-2-ylidenes and ethylene bridged imidazolidin-2-ylidenes were never isolated from deprotonation of the salts or reductive desulphurisation of the thiones. In situ reactions with the salts and palladium acetate resulted in decomposition. The synthesis of both enantiomers of 4,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxolane from tartaric acid enabled the preparation of chiral bridged diazolium salts and thiones. Neither the diimidazol-2-ylidenes nor the dibenzimidazol-2-ylidenes were isolated due to electronically stabilised carbenes being incompatible with the bridge. The diimidazolidin-2-thiones gave the free dicarbene when the N-substituent was the 2,6-diisopropylphenyl group with the 2,4,6-trimethylphenyl derivative giving the dimer. Ligand exchange complexation with the diimidazolidin-2-ylidene and dimer failed to provide a means to ruthenium and palladium chiral chelating complexes due to steric congestion. In situ studies of the salts gave the nine membered cis 4,5-bis(1-cyclohexylbenzimidazol-2-ylidene-3-methyl)-2,2-dimethyl-1,3-dioxolane palladium dibromide. Utilising both enantiomers of 4,5-bis(bromoethyl)-2,2-dimethyl-1,3-dioxolane, that were prepared through asymmetric dihydroxylation, allowed the synthesis of eleven membered ruthenium benzylidene complexes from stable solutions of diimidazol-2-ylidenes. Square planar trans palladium dibromide complexes were prepared through in situ methods using the 1-cyclohexyl and 1-phenylbenzimidazolium salts.

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30

Brown, Richard A. "The synthesis, structure and characterisation of some iron sandwich complexes and their application to organic synthesis." Thesis, University of Essex, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.332412.

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31

Evans, Jesse. "Synthesis of Rhenium and Manganese Pyridazoal Complexes." TopSCHOLAR®, 2013. http://digitalcommons.wku.edu/theses/1239.

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Pyridazines are a heterocyclic aromatic compound containing a characteristic N-N bond that are utilized in many fields, including medicine and electronics. It is this latter field that Dr. Snyder's research group is focused upon. Organometallic compounds are a better conducting material than the current inorganic compounds used in electronics due to better conductance of electricity, lower production cost, and the ability to be formed into thin films. With this in mind, Dr. Snyder's research group has set out to synthesize organometallic compounds for this purpose. Following procedures set forth by Snyder etc, and altered to form an off-metal route, we have successfully synthesized a library of fulvenes, Thalium Cp salts, 5,6 fused pyridazines, and pyridazial complexes. Thalium Cp salts were converted to Rhenium and Magnenese complexes through transmetalation. We have had success with the off-metal route at both higher yields and greater purity than the previous published on-metal route. These compounds have been fully characterized by 1H NMR, 13C NMR, IR, and Elemental Analysis. In addition, progress has been initiated to form Bromo Thiophene complexes following procedures set forth in Snyder, etc and modified for the off-metal route. However only fulvenes, pyridazine, and Thalium Cp salts have been synthesized and characterized by 1H NMR and 13C NMR.

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32

Davies, Stephen Robert. "Synthesis and characterisation of charge transfer complexes of new electron acceptors." Thesis, Durham University, 1989. http://etheses.dur.ac.uk/6507/.

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New electron acceptors, possessing various skeletal frameworks have been prepared and characterised. Complexation with a range of metal and organic cations reveal the suitability of the electron acceptors in the field of conducting charge-transfer complexes. Unsuccessful attempts to synthesise sterically demanding TCNQ derivatives, directly from the corresponding p-benzoquinone in the presence of titanium tetrachloride, provided a convenient route to a range of mono (dicyanomethylated)alkyl-p-benzoquinones, which were converted into N,7,7-tricyanoquinomethaneimine derivatives. Semi conducting charge-transfer salts of these new acceptors are described. Reduction of 2-dicyanomethylene-1,3-indandione (DCID) with cationic iodides, initiated a fascinating rearrangement to afford crystalline salts of the isomeric 2,3-dicyano-1,4-naphthoquinone (DCNQ), as confirmed by X-ray analysis.1,3-Metadinitrobenzene and 1,3,5-trinitrobenzene both form neutral, insulating, diamagnetic complexes with tetrathiafulvalene. The crystal structure of each complex is characterised by mixed stacks of alternate donor and acceptor molecules. The study of tetrachloro-DCID and l,3-bis(dicyanomethylene)indane further establishes that a wide range of electron acceptors belong in the development of organic metals.

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33

Vaughan, Richard Robert. "Synthesis and characterisation of cyclopentadienyl cobalt complexes of selenium-containing ligands." Thesis, Queen's University Belfast, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.334685.

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34

Marsden, C. "The synthesis and reactivity of di- and polynuclear mixed metal complexes." Thesis, University of Bristol, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.356224.

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35

Hanton, Martin John. "Coordination complexes of bidentate phosphino-imine ligands : synthesis, characterisation and reactivity." Thesis, University of Leicester, 2003. http://hdl.handle.net/2381/33724.

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This thesis describes the synthesis, reactivity and coordination chemistry of a range of bidentate phosphino-imine ligands. The reactivity of the resultant complexes is also probed, while testing of the complexes for catalytic activity in a range of carbon-carbon bond-forming reactions is documented. Chapter 1 introduces the concepts of 'hemi-lability' and 'trans-influence', along with heteroditopic bidentate ligands, and specifically examines imine- and phosphine-based ligands, particularly aminophosphines. The nature of the phosphorus centre in terms of its steric and electronic properties is surveyed, and the bonding of phosphines and imines with metals is discussed. A review of transition metal-catalysed olefin oligomerisation and polyketone formation then follows. Finally, the aims of this work are outlined. Chapter 2 introduces the PNP ligand {(Pri2N)2PCH2C(=NPri)CH2P(NPri2)2}, previously synthesized within the Dyer group. The reactivity and coordination chemistry of this ligand are then explored, and the reactivity of the resultant complexes probed. The complex [PdCl(Me)(PNP)] has been crystallographically characterised. Chapter 3 briefly introduces guanidines, before describing the synthesis of two new types of phosphino-imine ligand derived from bicyclic and acyclic guanidines {R2P(TBD), R = Ph, Mes, Pri 2N, Ph2N and Ph2P(DMC), respectively}. The reactivity and coordination chemistry of these ligands is then explored, with particular attention paid to the effects of varying the substituents at phosphorus in R2P(TBD). The reactivity of the resulting complexes is then documented. The molecular structures of the ligands Ph2P(TBD), (Pri2N)2P(TBD) and Ph2P(DMC), and of twenty of their complexes have been determined. Chapter 4 describes the synthesis of the new P.;N ligand Ph2P(2-IP). The reactivity and coordinationchemistry of this ligand is then appraised, as is the reactivity of the resulting complexes. The structures of four complexes of this ligand have been probed crystallographically, as has a serendipitously formed nickel complex. Chapter 5 documents the catalytic testing conducted, using the complexes prepared in the chapters 2-4.

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36

Jefferson, Gary Robert. "Synthesis and reactivity of enantiomerically enriched (arene) tricarbonyl chromium (0) complexes." Thesis, Imperial College London, 1997. http://hdl.handle.net/10044/1/11404.

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37

Poulton, Andrew Michael. "Investigation into the uses of bimetallic alkyne complexes in organic synthesis." Thesis, Loughborough University, 2005. https://dspace.lboro.ac.uk/2134/34566.

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This thesis describes the use of both heterobimetallic and novel desymmetrised homobimetallic metal alkyne complexes in organic chemistry. A range of novel desymmetrised Co2(CO)5IPr-alkyne complexes have been synthesised and their reactivity investigated. This resulted in a highly diastereoselective thermal Pauson–Khand reaction. Previous protocols in the literature have had to use N-oxide promoters to achieve diastereoselectivity on desymmetrised bis-cobalt cores. The use of substituted dihydrofurans as cyclopropane surrogates for the formation of novel homobimetallic 1,3-dipoles has been realised, although currently with high substrate specificity. The zinc mediated addition of carbon nucleophiles to the inherently chiral Co(CO)3MoCp(CO)2-alkyne core has been investigated. This overcomes a previous lack of reactivity towards carbon nucleophiles, but expresses only low diastereoselectivity. The use of the Co(CO)3MoCp(CO)2-alkyne core as a nucleophilic chiral auxiliary has been thoroughly investigated. Chapter 1: an overview of the Pauson–Khand and Nicholas reaction and developments in the field. Chapter 2 highlights our research into the use of bimetallic-alkyne complexes in organic synthesis. Chapter 3 provides experimental data for our experiments.

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38

Dopierala, Levi. "Synthesis and Characterization of some Thallium Salt Complexes." TopSCHOLAR®, 2014. http://digitalcommons.wku.edu/theses/1347.

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Research into conductive organic and organometallic polymers began in 1977 when Heeger, Macdiarmid, and Shirakawa first doped polyacteylene with Iodine. They found that this doping granted the polymer metallic properties increasing conductivity by 11 orders of magnitude.[1] Unfortunately, polyacteylene is highly air-sensitive making it difficult to work with and limiting its applications. Therefore, current research is focused on synthesizing new organic and organometallic conductive polymers. The drive to discover these new polymers stems from their application flexibility and their low production cost. Reported here is the synthesis of novel organometallic polymer precursors. Lead by Dr. Chad Snyder a library of chloro-phenyl based fulvenes, 5,6 fused ring pyridazines, and thallium Cp salts have successfully been synthesized. Research is currently underway to synthesize rhenium and manganese pyridazines through transmetalation of the thallium salts. The off-metal route of synthesis was followed as opposed to the previously reported on-metal route. Characterization was performed by 1H-NMR, 13CNMR, and IR. Additionally, research has begun on bromo-thiophene complexes. So far, bromothiophene fulvenes, pyridazines, and thallium Cp salts have been synthesized and work is currently underway to produced rhenium and manganese pyridazines as well. Characterization was performed by 1H-NMR and 13C-NMR.

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39

Kowalski, Vincent Michael. "Synthesis and Characterization of Dipyrromethene Complexes of Antimony." University of Toledo / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1493393079741153.

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40

Cragg-Hine, Ian. "Early main group metal complexes of multi-functional organic molecules." Thesis, University of Cambridge, 1995. https://www.repository.cam.ac.uk/handle/1810/271932.

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41

Greenacre, Victoria. "Synthesis and chemistry of novel ambiphilic phosphorus based ligands and complexes." Thesis, University of Sussex, 2017. http://sro.sussex.ac.uk/id/eprint/66736/.

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The chemistry of ambiphilic molecules, such as phosphine-boranes, has experienced a resurgence in interest, in part due to the emergence of Frustrated Lewis Pairs (FLPs). With a 2-atom bridge to separate the phosphine and borane units, the unsaturated, 1-borata-4-phosphoniacyclobut-2-enes R2BC(R)=C(Ph)PPh2 have been investigated. Their solid state data has been complemented by DFT studies, with a view towards controlling the geometry around a metal centre in order to position the Lewis acid unit over the Lewis basic metal centre without forming an adduct. The reactivity of the saturated and unsaturated phosphine-boranes has been also probed with a series of Lewis-basic metals. It was found that while the saturated systems readily coordinate to group 9 and 10 metals, the phosphorus-boron bond of the unsaturated systems remains too strong for coordination. Therefore, attempts to disrupt the strong P-B bond were made using pyridine. Phosphaalkynes of the type RMe2SiC≡P have been prepared from RSiMe2CH2Cl, by converting the 'CH2Cl' unit into 'CH2PCl2', before dehydrochlorination. The ruthenaphosphaalkenyls [Ru{P=CH(SiMe2R)}Cl(CO)(PPh3)2] are then prepared in high yield from the corresponding phosphaalkynes (P≡CSiMe2R, R = Ph, tolyl, nBu, p-CF3-C6H4) through hydroruthenation with [RuHCl(CO)(PPh3)3]. The first solid-state structural data of these ruthenaphosphaalkenyls is described and complemented by DFT studies of the precedent [Ru(P=CHtBu)Cl(CO)(PPh3)2)] alongside silyl based systems, allowing the visualisation of molecular orbitals and calculated NMR data. The silyl systems mimic the previously reported propensity toward electrophilic addition shown by Ru{P=CH(tBu)}Cl(CO)(PPh3)2]. However, the presence of the silyl group also appears to modify the reactivity compared to that previously published for [Ru{P=CH(tBu)}Cl(CO)(PPh3)2]; demonstrated by the addition of HCl to form the saturated P-C linkage shown in [RuCl2(CO)(PPh3)2{P(HCl)CH2SiMe2R}]. The ruthenaphosphaalkenes also exhibit reactivity with nucleophiles (pyrazolates) to form novel bridging pyrazolyl η2–phosphaalkenic compounds of the type [Ru(CO){κ3-N,C,P-P(PzR',R")CH(SiMe2R)}(PPh3)2], building on earlier work within the group.

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42

Lynam, Jason Martin. "Vinyl ketone and vinyl aldehyde complexes of ruthenium." Thesis, University of York, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.265558.

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43

Martin, Jeff. "The synthesis and characterisation of novel ferrocene ligands and their metal complexes." Thesis, Imperial College London, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.313662.

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44

Armstrong, Elaine M. "The synthesis and reactions of molybdenum(II) and tungsten(II) alkyne complexes." Thesis, Bangor University, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.314395.

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45

Chaudhary, Soraya Shezana. "Synthesis of some nitrogen-donor macrocycles and their complexes with metal ions." Thesis, London Metropolitan University, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.287567.

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46

Chakrabarti, Jayatibha. "Metal complexes of 1,2 quinone monooximes and their applications in organic synthesis." Thesis, London Metropolitan University, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.294986.

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Systematic investigations of the reactions of 1,2-quinone monooximes (qoH) with alkali (lithium, sodium and potassium) and alkaline earth metal (magnesium and barium) hydroxides and acetates [M(OH)n or M(OAc)r] have been carried out. In the case of 1,2-naphthaquinone 1-oxime (1-nqoH) and 1,2-naphthaquinone 2-oxime (2- nqoH), all the alkali metals form complexes of types M(qo). nS and M(qo)(qoH)(S) [S = H20 or EtOH]. M(qo). nS arises when a reactant molar ratio [MOH: qoH] of 1: 1 is used whereas M(qo)(qoH)(S) is formed when the ratio is 1: 2 or 1: 3. An analogous behaviour is also observed in the reactions of NaOH and KOH with 5- ethylamino-4-methyl-1,2-benzoquinone 2-oxime (5-Et-4-MeqoH). The reaction of LiOH with 5-Et-4-MeqoH in the ratio of 1: 1 gives Li(go)(qoH)(H20) whereas using molar ratios of 1: 2 and 1: >_ 3 give Li(go)(qoH),. 1' H20. The alkaline earth metals form complexes of type M(go)2.2H20 with 1-nqoH and 5-Et-4-MeqoH. Complexes of type M(Mpo). nS and M(Mpo)(MpoH). S [M = Li, Na, K], M(Mpo)2.2H20 and M(1-Ppo),. 2H; 0 [M = Mg and Ba] result from the reactions of MOH, Ba(OH)2 and Mg(OAc), with 1,3-dimethyl-lH-pyrazole-4,5-dione-4-oxime (MpoH) and 3-methyl- 1-phenyl-lH-pyrazole-4,5-dione-4-oximes (1-PpoH). Structural investigations of the qoH complexes noted above were carried out using spectroscopic, magnetochemical and X-ray crystallographic studies. All the complexes exhibit association as indicated by LSIMS. Their IR spectra indicate the quinone oximic character of the ligands and the involvement of the carbonyl group in the bonding of the ligand to the metal atom. X-ray studies of the lithium and sodium complexes of 5-Et-4-MeqoH show that the ligand chelates to the metal atom through the nitrogen atom of the oxime group and the oxygen atom of the carbonyl group and suggest that its structure can be best described as an intermediate between the quinone oxime and imino oxime form. In the bis-chelates, the metal atom is penta coordinated whereas hexa coordination is shown by Li(go)(qoH)2. IR studies of the complexes ML, [M = Mn, Ni, Cu and Zn; LH = 1-PpoH and MpoH] and their aquo and pyridine adducts indicate that the ligand exists essentially in the oximic form. The lack of reaction between these complexes and triphenylphosphine suggests that the oxygen atom of the NO group is involved in bonding to the metal atom. This feature is confirmed by the X-ray studies of Zn(Mpo)2(H, O)2 and Mn(1-Ppo)2(py)2 which indicate the presence of six-membered chelate rings and octahedral coordination around the metal atom. Magnetic moment determinations of the aquo and pyridine adducts show that the compounds are magnetically dilute and hence monomeric in the solid state. The lowering of magnetic moment observed for anhydrous complexes is accounted for in terms of association. Support for association is also obtained from the LSIM spectra which show dimetallic and trimetallic species in their spectra. The lithium, sodium and barium complexes of 1-ngoH react with dimethyl acetylenedicarboxylate (DMAD) at -75-50° to give the open chain adduct, O-(1', 2'- dicarbomethoxyethenyl)-1,2-naphthaquinone1 -oxime. Open chain adduct formation is also observed in the reactions of pyrazole-4,5-dione-4-oximes or their lithium complexes with DMAD at 0-40°C. At higher temperatures the reactions lead to Schiff Base type condensation products whose formation is accounted mechanistically in terms of the deoxygenation of the oxime group.

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47

Hasan, Md Faruque. "Synthesis and Characterization of Cobalt-Based Coordination Complexes with Various Organic Linkers." Youngstown State University / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=ysu1532001654030436.

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48

Chanthateyanonth, Ratana. "Application of dendronized-metal complexes on silica as catalysts for organic synthesis." Thesis, University of Ottawa (Canada), 2004. http://hdl.handle.net/10393/29085.

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This thesis describes a variety of synthetic attempts to prepare dendrimer-metal complexes anchored to silica. The new complexes were obtained by immobilization of a tridentate diphosphinoaryl ligand (PCP-type) palladium(II) complex onto silica and silica supported dendrimers which combine the advantages of heterogeneous and homogeneous catalysts. They are thermally stable and they are also stable towards oxygen and moisture. These complexes show high catalytic activity for the Heck reaction of aryl iodides with styrene and n-butyl acrylate, resulting in high yields of stilbene and cinnamate ester. They are also active in the reactions of a variety of aryl bromides with n-butyl and methyl acrylate, providing para-substituted cinnamate esters in good yields. These complexes are also effective catalysts for the cyclocarbonylation reaction of 2-allylphenol yielding five- or seven-membered ring lactones in good selectivity and in high yields. In addition, these complexes can be recycled by simple filtration in air and reused with little to moderate loss of activity. In both kinds of reactions, the dendritic systems show higher activity compared to the non-dendritic systems.

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49

Scott, Joseph Brian. "Synthesis and Characterization of Some Rhenium Complexes." TopSCHOLAR®, 2009. http://digitalcommons.wku.edu/theses/114.

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Plastics or polymers are thought to behave oppositely from metals. Ideally, polymers behave as insulators while metals conduct electricity. Shirakawa and coworkers discovered conductive polymers in 1977.1 These conductor polymers have been extensively studied, discovering that charge transfer oxidative doping of polyacteylene could increase its conductivity by 12 orders of magnitude. Polyacetylene, although showing promise as an organic conductor, because it is highly air-sensitive and oxidizes when exposed to molecular oxygen, therefore making this an unattractive use for commercial products. Attention has been focused on heterocylic aromatic polymers such as polythiophene and polypyrrole, in efforts to produce conductive polymers that are air-stable, tractable, and have a low band gap. The lone-pair electrons of the sulfur and nitrogen atoms tend to stabilize the positive charges of the p-doped polymers through resonance. 2 By using Shirakawas’ idea of using polypyrrole as the focus point of our research and expanding upon that by the addition of a rhenium metal to an organic compound, (1,2-C5H3(CNR)2) and this should offer some new and interesting chemical properties. These new properties are; new optical properties, new electronic properties, improved physical properties, and a reversible electrochemical shift. This research will help in the field of organometallic semiconductors in applications such as OLED’s, and electrochromic windows.3-6

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Guest, Daniel P. "Synthesis of novel N-heterocyclic carbene-palladium complexes and their catalytic activity." Thesis, University of Sussex, 2017. http://sro.sussex.ac.uk/id/eprint/68087/.

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Chapter 1: Gives the reader a background on carbenes paying particular attention to N-heterocyclic carbenes (NHCs). The chapter describes NHC's electronic and structural properties and their behaviour as ligands. The recent usage of NHC-palladium complexes as catalysts for cross-coupling reactions is explored. Chapter 2: Provides a background on NHC-palladium complexes bearing N-donors as throwaway ligands, highlighting the importance of throw-away ligands on catalytic activity. The chapter describes the preparation of a number of novel NHC-palladium complexes bearing throw-away ligands and the activity of (IPr*)PdCl2(TEA) in Buchwald-Hartwig aminations is explored. Chapter 3: Provides a background on the Mizoroki Heck reaction, focusing on the importance of charged intermediates in the process. Then reviews the current development of anionic NHC-palladium complexes in the literature. An account of the discovery and preparation of novel [(NHC)PdCl3[TBA] complexes and the catalytic activity of [(SIPr)PdCl3[TBA] in Mizoroki-Heck coupling reactions is given. A plausible Amotore-Jutand type mechanism is proposed which is supported by DFT calculations provided by research collaborators. Chapter 4: Provides a background on C-H activation reactions catalysed by palladium compounds with particular focus on acetoxylation reactions. The chapter describes the synthesis of [(NHC)PdCl2X][Y] complexes including the development of [(IMes)PdCl2OAc][TBA] and its performance in acetoxylation reactions. A proposed mechanism for the reaction of [(IMes)PdCl2OAc][TBA] is discussed, using experimental observations.

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