Dissertations / Theses: 'Tridentate Ligands - Metal Complexes'

1

Harkup, Kathryn. "Studies in tridentate hemilabile ligands and their metal complexes." Thesis, University of Nottingham, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.406977.

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2

Chung, Simon S. M. "Transition metal complexes of new mixed donor tridentate ligands." Thesis, University of Nottingham, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.367415.

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3

Paine, Tapan Kanti. "Transition metal complexes of tridentate bisphenol ligands and their reactivity towards organic substrate." [S.l. : s.n.], 2002. http://deposit.ddb.de/cgi-bin/dokserv?idn=967431786.

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4

Nobbs, James. "Complexes Bearing Tridentate Heterocyclic Ligands in Transition Metal Catalysed Olefin and Diolefin Polymerisation." Thesis, Imperial College London, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.525226.

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5

Tam, Ka-ho. "Group 4 complexes bearing tridentate aryloxide-based ancillary ligands synthesis, characterization and application as olefin polymerization catalysts /." Click to view the E-thesis via HKUTO, 2006. http://sunzi.lib.hku.hk/hkuto/record/B36727222.

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6

Tam, Ka-ho, and 譚家豪. "Group 4 complexes bearing tridentate aryloxide-based ancillaryligands: synthesis, characterization andapplication as olefin polymerization catalysts." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2006. http://hub.hku.hk/bib/B36727222.

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7

Dankhoff, Katja [Verfasser], and Birgit [Akademischer Betreuer] Weber. "Transition metal complexes with tridentate ligands : a variety of properties / Katja Dankhoff ; Betreuer: Birgit Weber." Bayreuth : Universität Bayreuth, 2019. http://d-nb.info/1198308826/34.

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8

Liang, Lan-Chang 1967. "Early transition metal complexes containing tridentate amido ligands : a systematic approach to Ziegler-Natta catalysis." Thesis, Massachusetts Institute of Technology, 1999. http://hdl.handle.net/1721.1/85341.

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9

Williams, Dara Bridget. "Tridentate, dianionic ligands for alkane functionalization with platinum(II) and oxidation of iridium(III) hydrides with dioxygen /." Thesis, Connect to this title online; UW restricted, 2007. http://hdl.handle.net/1773/8545.

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10

Chow, Pui-keong, and 周沛強. "Luminescent palladium(II) and platinum(II) complexes with tridentate monoanionic and tetradentate dianionic cyclometallated ligands : structures, photophysical properties and material application." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2013. http://hdl.handle.net/10722/193416.

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Four structural isomers of platinum(II) complexes with C-deprotonated R-C^N^N-R’ cyclometallated ligands (R-C^N^N-R’ = -extended 6-aryl-2,2’-bipyridine derivatives containing 2-naphthyl, 3-isoquinolinyl, 1-isoquinolinyl or 2-quinolinyl moieties) have been synthesized with their photophysical properties investigated. The one bearing a 3-isoquinolinyl moiety shows the highest emission quantum yield among the four and hence has been extensively modified to give a series of complexes with different ancillary ligands (chloride, iodide, phenoxide, or acetylide). Most of these complexes show vibronic emission (max = 515–644 nm) with high emission quantum yield (up to unity) in degassed CH2Cl2; one of them has been used for OLED fabrication and shows a maximum EQE of 8.15 % with current efficiency of 25 cd A–1. The photocatalytic properties of these derivative complexes for oxidative tertiary amine functionalization have also been examined. Several highly robust and emissive platinum(II) complexes supported by two types of tetradentate O^N^C^N ligand systems (Φem up to 0.99; Td up to 520 ℃) have been synthesized and show different emission energies (λmax = 482–561 nm). Most of them exhibit excimeric emission in solution state at room temperature which are dependent on the modifications on the tetradentate O^N^C^N ligands. DFT/TDDFT calculations reveal that the metal complex showing the most intense excimeric emission possesses an excimeric excited state with a localized structure, which is unusual for these classes of platinum(II) complexes. Based on this finding, WOLED (ηL(max) = 71.0 cd/A, ηp(max) = 55.8 lm/W, ηExt = 16.5 %, CIE = 0.33, 0.42, CRI = 77) and WPLED (ηL(max) = 17.0 cd/A, ηp(max) = 9.1 lm/W, ηExt = 9.7 %, CIE = 0.43, 0.45, CRI = 78) based on this complex have been fabricated with high efficiency achieved. Palladium(II) complexes containing C-deprotonated R-C^N^N-R’ cyclometallated and pentafluorophenylacetylide ligands exhibit phosphorescence in both solid state and fluid solutions at room temperature with some of them exhibiting aggregation-induced emission (AIE). These complexes have been applied as photosensitizers in light-induced oxidative functionalization of secondary and tertiary benzylic amines as well as in light-induced hydrogen production, with a maximum of 175 turnovers for hydrogen produced. Palladium(II) complexes containing two types of tetradentate dianionic O^N^C^N ligand systems (Systems 1 and 2) have been prepared and show constrasting photophyical properties. A full scale time-resolved spectroscopic analysis has been done on some of these complexes and a platinum(II) analogue. These complexes are found to have similar excited state decay pathway( 〖S_1〗^i→〖S_1〗^f→T) with ΦISC of about unity. The emission efficiency of System 2 complexes is superior to that of System 1 complexes, which is ascribed to the suppression of excited state distortion on the basis of the results of DFT calculations. A lower radiative decay rate of System 2 palladium(II) complexes relative to the platinum(II) analogue has been found, which could be due to their lower spin-orbit coupling constant. One of the palladium(II) complexes has been applied in vacuum-deposited OLEDs with maximum current density, power efficiency and EQE of 20.0 cd A^(-1), 13.6 lm W^(-1) and 7.4 % respectively. In addition, applications of these palladium(II) complexes as photosensitizers for oxidation of secondary amines have been examined.
published_or_final_version
Chemistry
Doctoral
Doctor of Philosophy

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11

Duncan, Nathan C. Garner Charles M. "Tridentate nitrogen ligands derived from 2,6-bis-hydrazinopyridine (BHP) preparation and study of the 2,6-bis-hydrasonopyridines, 2, 6-bis-pyrazolylpytidines, and 2,6-bis-indazolylpyridines /." Waco, Tex. : Baylor University, 2009. http://hdl.handle.net/2104/5320.

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12

Phillips, Scott D. "Enantioselective hydrogenation using ruthenium complexes of tridentate ligands." Thesis, University of St Andrews, 2011. http://hdl.handle.net/10023/1915.

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This thesis describes the development of the [RuCl₂(P N N)L] catalytic system for asymmetric hydrogenation. It has been demonstrated that the current system is efficient in preparing a range of bulky chiral alcohols in good enantioselectivity, many of which are likely to be inaccessible using the more classic [RuCl₂(P P)N N)] system developed by Noyori and coworkers. It has been shown that the current system is tolerant of a range of substrate electronic effects as well as the presence of heteroaromatic functionality, thus showing its applicability in synthesis. This has been extended to prepare a number of bulky derivatives of synthetically important molecules. The demonstration of this is significant as in drug design, for example, studies that aim to extend lipophilicity or steric bulk make the ability to prepare alcohols across the full range of steric properties important. We have shown that chiral alcohols with adjacent gem-dimethyl groups can be prepared in high enantioselectivity and their conversion into other valuable molecules, such as chiral lactones has been demonstrated. Detailed mechanistic studies have been undertaken for the present system in order to aid rational design of new, more active and selective catalysts. A number of achiral variants of the original system have been prepared and the key features of ligand structure for efficient catalysis have been identified. This was accomplished by rigorous kinetic analysis of each complex, using specialist gas-uptake monitoring equipment. The key features of catalyst structure and optimal reaction conditions for efficient asymmetric hydrogenation have been identified. Our greater understanding of the present system allowed us to rationally design new catalysts of for enantioselective hydrogenation. Our aim was to be able to tune the catalyst structure to carry out hydrogenation of a greater variety of ketone substrate with high activity and selectivity. We have successfully prepared second generation catalysts that show enhanced enantioselectivity for a variety of substrates, many of which were problematic with the Noyori system.

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13

Muresan, Nicoleta Mihaela. "Unusual main group element complexes with tridentate diketoamine ligands." [S.l.] : [s.n.], 2005. http://deposit.ddb.de/cgi-bin/dokserv?idn=974319775.

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14

Nambukara, Wellala Nadeesha P. "Synthesis and Catalytic Activities of Nickel Complexes Bearing Flexible Tridentate Ligands." University of Cincinnati / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1491561548324255.

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15

Baumann, Robert 1973. "Group 4 complexes containing tridentate diamido donor ligands : organometallic chemistry and catalysis." Thesis, Massachusetts Institute of Technology, 1998. http://hdl.handle.net/1721.1/85239.

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16

Onyiriuka, Emmanuel C. "Pyrazolyl ligands in mixed metal complexes." Thesis, University of British Columbia, 1986. http://hdl.handle.net/2429/27178.

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The anions LMo(CO)₃⁻ (L = MeGapz₃ or MeGa(3,5-Me₂pz)₃) have been isolated as the Na⁺, Et₄N⁺ or HAsPh₃⁺ salts and the solution structures of the Na⁺ salts in THF have been defined by analysis of the v[sub CO] ir spectra. Ion-pair interaction of the LMo(CO)₃⁻ anion with Na⁺cation in THF solution is apparent from the spectroscopic evidence obtained. The MeGapz₃Mo(CO)₃ ⁻anion reacted with HCl or EtBr to give the seven-coordinate [MeGapz₃]-Mo(CO)₃R (R = H or Et) complexes. However, with Mel or PhCOCl complexes of the type [MeGapz₃]Mo(CO)₂(n₂-COR) (R = Me or Ph) were obtained. The reactions of the LMo(CO)₃⁻ ions (L = MeGapz₃ HBpz₃ or Me₂Gapz(0-CH₂CH₂NMe₂)) with a variety of transition metal halide species have yielded complexes with transition metal-transition metal bonds. The X-ray crystal structures of two such complexes [MeGapz₃]Mo(CO)₃Cu(PPh₃) and [MeGapz₃]Mo-(CO)₃Rh(PPh₃)₂ have been determined. The former complex provides a rare example of a 3:3:1, or capped octahedral structure, with a short (mean) Mo-Cu distance of 2.513(9)Å. The latter compound displays one terminal and two bridging CO ligands and a Mo-Rh distance of 2.6066(5)Å. Transition metal-group 14 (Si, Ge or Sn) element bonded complexes of the type [MeGapz₃]Mo(CO) ₃M'Y (Y = Me₃ or Ph₃, M' = Ge or Sn; Y = Me₃, M' = Si; Y = Me₂Cl, M' = Sn) have been prepared from the reaction of the MeGapz₃Mo(CO)₃anion with the appropriate organo-group 14 chloride. In all the complexes, direct Mo-M' (M' = Si, Ge or Sn) single bonds are featured. The [MeGapz₃]Mo(CO) ₃SnMe₂Cl complex shows an interesting solution behaviour in which a transition from a 3:4, or piano stool structure, to a 3:3:1, or capped octahedral arrangement, is thought to occur. The 3:3:1 structure has been demonstrated in the solid state for the [MeGapz₃]Mo(CO)₃SnPh₃ compound by means of a crystal structure determination. The 'Mo-SnPh₃' and the 'Mo-Cu' compounds discussed in this work are the first examples of such complexes incorporating either the MeGapz₃⁻, HBpz₃⁻ or C₅H₅⁻ ligands in which the 3:3:1 arrangement has been demonstrated unequivocally. The novel tridentate unsymmetric ligands Me₂GapzO(C₅H₃N)CH₂NMe₂⁻ (L[sub a]⁻) and Me₂GapzO(C₉H₆N)⁻ (L[sub q]⁻) have been prepared and numerous transition metal compounds containing these ligands synthesized. The compounds L[sub a] M(CO)₃(M = Mn or Re) are the first examples of transition metal carbonyl complexes in which both the fac and mer arrangements of the unsymmetric ligand about the central metal have been found to co-exist in solution. The square planar rhodium(I) complex, L[sub q]Rh(CO) has been shown to add Mel oxidatively, followed by facile methyl migration reaction to produce the five-coordinate Rh(III) acetyl derivative, L[sub q]Rh(COMe)I. In contrast, the reaction of L[sub a]Rh(CO) with Mel, led to the six-coordinate Rh(III) oxidative addition product, L[sub a]Rh(Me)(I)CO.
Science, Faculty of
Chemistry, Department of
Graduate

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17

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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18

McHugh, Paul. "Oligonuclear metal complexes of compartmental ligands." Thesis, University of Sheffield, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.408313.

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19

Crofts, Rhona D. "Platinum metal complexes of macrocyclic ligands." Thesis, University of Edinburgh, 1995. http://hdl.handle.net/1842/13493.

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20

Whitman, Rachel A. "DNA Interactions of Bimetallic Ruthenium Complexes Containing Tridentate Ligands with Extended p-Systems." The Ohio State University, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=osu1409061017.

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21

Yan, Jing, and 严静. "The anticancer properties of gold (III) complexes with tridentate cyclometalated, porphyrinato and glycosylated ligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2011. http://hub.hku.hk/bib/B4587265X.

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22

Humphrey, Elizabeth Rebecca. "Tris(pyrazolyl)borate metal complexes : new ligands and metal-metal interactions." Thesis, University of Bristol, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.340301.

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23

Landman, Marile. "Synthesis of metal complexes with thiophene ligands." Thesis, Access to E-Thesis, 2000. http://upetd.up.ac.za/thesis/available/etd-12042006-143722/.

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24

Olson, Michael David. "Pyrazolyl based ligands in transition metal complexes." Thesis, University of British Columbia, 1989. http://hdl.handle.net/2429/27610.

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Several uninegative/ multidentate pyrazolyl based ligands were synthesized [eg. HBPZ₃₋, HBpz”₃₋, MeGapz₃₋/ MeGapz” ₃₋, H2BpZ₂₋/ Me2Bpz₂₋/ Me2GapZ₂₋/ Me2Gapz"₂₋/ Me₂Gapz(OCH₂CH₂NH₂)⁻Me₂Gapz(OCH₂CH₂CH=CH₂)⁻ ; pz pyrazolyl/ pz" = 3, 5 dimethylpyrazolyl]. These ligands were reacted with the sterically hindered metal complex, HBpz*₃MCl (M = Co, Ni; pz* = 3-iPr-4-Br-pyrazolyl) and the mixed-ligand transition metal complexes of general formulae, HBpz*₃ML, were isolated. The X-ray crystal structure of one such complex, HBpz*₃Nipz"₃BH was determined showing a near octahedral arrangement of ligands about the nickel centre. The electronic spectra of the nickel complexes were recorded and compared to predicted transitions. The electronic spectra of the four coordinate nickel complex, HBpz*₃NiCl, fit a d⁸, tetrahedral, ligand field model. The six coordinate complexes, HBpz*₃NiL (L = HBPZ₃, HBpz"₃, MeGapz₃, MeGapz”₃), fit a d⁸, octahedral, ligand field model. The unsymmetrical pyrazolylgallate ligands were reacted with the rhodium dimer [Rh(CO)₂CI]₂ to give the square planar complexes, LRh(CO) [L = Me2Gapz(OCH₂CH₂NH₂), Me₂Gapz(OCH₂CH₂CH=CH₂)]. These rhodium[I] complexes appeared to undergo oxidative additions of Mel, allylbromide and I₂. Furthermore these rhodium[I] complexes appeared to bind the small gas molecules, CO and ethene. A number of heterobimetallic complexes, with direct metal-metal bonds, were prepared and isolated from the reaction of the molybdenum anion, HBpz"₃(CO)₃MO⁻ with the transition metal halides, [CuPPb₃Cl]₄, SnR₃Cl (R = Me, Ph) and GePh₃Cl.
Science, Faculty of
Chemistry, Department of
Graduate

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25

Graham, Todd Warren. "Mixed-metal complexes incorporating polydentate bridging ligands." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0028/NQ39533.pdf.

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26

Skinner, Michael E. G. "Transition metal complexes of diamide-diamine ligands." Thesis, University of Oxford, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.365390.

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27

Niven, Stuart. "Chelating carbene ligands and their metal complexes." Thesis, Cardiff University, 2007. http://orca.cf.ac.uk/54628/.

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This thesis describes the synthesis of a number of functionalised imidazolium salts as precursors to N- heterocyclic carbenes and their subsequent coordination to Ag and Pd. Further a number of the Pd complexes were tested in the Heck reaction and their activities compared to complexes with similar structural features currently within the literature. A range of imidazolium salts have been synthesised which include quinoline and octahydroacridine moieties and have been characterised by a number of methods including X-ray crystallography. A bis imidazolium salt has also been prepared as a DIOP analogue. The imidazolium salts were successfully reacted with Ag20 to form the NHCAg(I) complexes. The quinoline and octahydroacridine based NHCs were transmetallated to Pd as chelating ligands, the quinoline based systems appearing as planar, strained complexes in the X-ray structure. The activities of the quinoline and octahydroacridine based NHCPd(II) complexes in the Heck coupling of 4-bromoacetophenone and 4-chlorobenzaldehyde with n-butyl acrylate were assessed and found to be comparable to similar systems with low to satisfactory conversions.

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28

O'Shaughnessy, Paul. "Alkali metal complexes of phosphorus donor ligands." Thesis, University of Newcastle Upon Tyne, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.323668.

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29

Okey, J. N. "Metal complexes of nitrogen-donor heteroaromatic ligands." Thesis, Imperial College London, 1987. http://hdl.handle.net/10044/1/47492.

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30

Seidel, Scott William 1971. "Transition metal complexes containing chelating amido ligands." Thesis, Massachusetts Institute of Technology, 1998. http://hdl.handle.net/1721.1/47411.

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31

Lam, Chong Ho. "Metal complexes containing oxygen tripod ligands : models of metal oxides /." View Abstract or Full-Text, 2003. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202003%20LAMC.

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Thesis (Ph. D.)--Hong Kong University of Science and Technology, 2003.
Includes bibliographical references (leaves 275-290). Also available in electronic version. Access restricted to campus users.

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32

Dubberley, Stuart R. "New calix[4]arene metal complexes." Thesis, University of Oxford, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.365290.

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33

Burgess, Michael Graeme. "Metal Complexes of Acyclic and Macrocyclic Multifunctional Ligands." Thesis, University of Auckland, 2008. http://hdl.handle.net/2292/5171.

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This thesis describes the design, synthesis and study of metal derivatives of new acyclic and macrocyclic ligands containing pyridine and amide groups. Chapter 1 provides an overview of metal-carboxamide and pyridinamide chemistry including a number of important pincer compounds, macrocyclic involvement in formation of metal-templated rotaxanes and catenanes, oxidation catalysts, anion receptors and bimetallic complexes. Chapter 2 discusses new palladium(II) complexes of an acyclic ligand bearing pendant 2-pyridyl-6-methyl arms, N,N_-bis(6-methyl-2-pyridinyl)-2,6-pyridinedicarboxamide (H2LMe). H2LMe formed a dimer [Pd(LMe)]2 when treated with palladium(II) salts and non-ligating bases, but in the presence of DBU the palladium-DBU adduct, Pd(LMe)(DBU), was formed. Reaction of Pd(LMe)(DBU) with methyl iodide resulted in the displacement of the DBU ligand and the concomitant formation of cationic monomeric complex, [PdI(LMe{Me}2)]I and dimeric N-methylpyridinium complex, [Pd(LMe{Me})]2I2. A series of ligands, N,N_-bis(x-tolyl)-2,6-pyridinedicarboxamide (x = 2, 3, 4) (H2Lxtol), bearing ortho-, meta- and para-tolyl groups, was prepared and these were coordinated to palladium(II) in their deprotonated form so that the effect of the pendant pyridine rings and steric environment around the metal on the reactivity of metal derivatives could be investigated. Stable palladium(II) derivatives of the deprotonated H2Lxtol ligands, Pd(Lxtol)(E) (E = DBU, n-butylamine, p-tolylisocyanide) were prepared. The p-tolylisocyanide adducts reacted with pyrrolidine or p-toluidine to afford the stable bis(amino)carbene complexes, Pd(Lxtol)(=C(NH-p-tolyl)(pyrl)) and Pd(Lxtol)(=C(NH-p-tolyl)2), respectively. The coordinated DBU ligands in Pd(Lxtol)(DBU) and Pd(LMe)(DBU) were displaced by n-butylamine to afford the corresponding n-butylamine adducts, and their relative rates of exchange were determined by 1H NMR spectroscopy. Chapter 3 discusses palladium(II) complexes of dicationic N-methylpyridinium ligands prepared by treating H2LMe or the series of ligands, N,N_-bis(x-pyridinyl)-2,6- pyridinedicarboxamide (x = 2, 3, 4) (H2Lxpy) that contain pendant 2-, 3-, or 4-pyridyl groups, with methyl triflate to form [H2LMe{Me}2][OTf]2 or [H2Lxpy{Me}2][OTf]2, respectively. These ligands were coordinated in their deprotonated forms to palladium(II) to give [PdCl(Lxpy{Me}2)]OTf. The chloro ligands in these metallated complexes were displaced on treatment with silver triflate in acetonitrile or water to afford the corresponding solvent adducts. The coordinated solvent molecules in [Pd(LMe{Me}2)(NCCH3)][OTf]2 and [Pd(Lopy{Me}2)(OH2)][OTf]2 could in turn be displaced by p-tolylisocyanide to form isocyanide adducts, [Pd(LMe{Me}2)(CN-ptolyl)][ OTf]2 and [Pd(Lopy{Me}2)(CN-p-tolyl)][OTf]2. Dicationic bis(amino)carbene complexes [Pd(LMe{Me}2)(=C(NH-p-tolyl)2)][OTf]2 and [Pd(Lopy{Me}2)(=C(NH-ptolyl) 2)][OTf]2 were prepared by treating the corresponding isocyanide precursors with p-toluidine. A 1H NMR spectroscopic study was performed to compare the relative rates of reaction of p-toluidine with the neutral tolyl isocyanide complexes Pd(Lxtol)(CN-p-tolyl) and the dicationic isocyanide complexes [Pd(LMe{Me}2)(CN-ptolyl)][ OTf]2 and [Pd(Lopy{Me}2)(CN-p-tolyl)][OTf]2 to determine the influence of the steric and electronic environments on the reactivity of the isocyanide ligand. On deprotonation of the amide groups in [H2LMe{Me}2][OTf]2 and [H2Lopy{Me}2][OTf]2 the neutral free bis(imine) compounds LMe{Me}2 and Lopy{Me}2 could be isolated. Chapter 4 discusses extended acyclic ligands H4LpdnA and H4LSpyA (H4LxA) that were derived from the precursor N,N_-bis(6-acrylamido-2-pyridinyl)pyridine-2,6- dicarboxamide (H4LacrA) through Michael addition of pyrrolidine or 2- mercaptopyridine, respectively, to the acrylyl groups. The double-helical dimers [M(H2LxA)]2 were formed when these ligands were treated with palladium(II) or mercury(II) acetate, and in the presence of DBU the adducts Pd(H2LxA)(DBU) were formed. In the absence of added base, palladium(II) acetate coordinated between the tail amine groups of the ligand H4LpdnA which bears terminal pyrrolidyl groups. Chapter 5 discusses complexes of macrocycles formed from double Michael-type addition of the amines n-butylamine, 2-(aminomethyl)pyridine, 2-(aminoethyl)pyridine, N,N-dimethylethylenediamine and N,N_-bis(2-pyridylmethyl)ethylenediamine to the pendant acrylyl groups of H4LacrA. The macrocycle synthesised from addition of nbutylamine, H4LnBu, reacted with palladium(II) acetate and DBU to form a complex in which palladium was coordinated in the macrocycle headgroup and an aminolactam resulting from hydrolysis of DBU was coordinated on the fourth site of the metal, Pd(H2LnBu)(NH2Lac[7]). A palladium derivative of H4LnBu with a labile water ligand, Pd(H2LnBu)(OH2), was prepared and used for subsequent syntheses of n-butylamine, DBU and p-tolylisocyanide adducts. When treated with p-toluidine, the isocyanide ligand of the macrocyclic p-tolylisocyanide adduct was displaced to form a p-toluidine adduct. Modified macrocycles with other amine donors incorporated into the tail were prepared in order to provide an additional site for metal complexation. The macrocycle with an additional N,N-dimethylamino group, H4Ldmen, reacted with metal salts to form complexes where metallation had taken place at the tail amide groups and the tail amine group interacted with the metal.

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34

Lawrence, Sally. "Early transition metal complexes of pyrazole-derived ligands." Thesis, University of Oxford, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.433560.

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35

Franks, Mark A. "Transition metal complexes containing phenylthiolate and phenolate ligands." Thesis, University of Nottingham, 2011. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.580393.

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Chapter 1 provides an introduction to metalloenzymes that either feature active sites containing Ni-thiolate ligation or utilise phenoxyl radicals to perform their catalytic function, with a particular emphasis on the enzymatic active sites of Ni-containing superoxide dismutase (Ni SOD), [NiFe] hydrogenase and galactose oxidase. Studies concerning low molecular weight complexes of each active site are reviewed and their relevance with respect to enzyme function discussed. Details of the project outline conclude the chapter. Chapter 2 details the syntheses and characterisation of the [Zn(tsalen)] derived complexes [ZneBuLsC3N)], [ZneBuLsC2N)], [ZneBuLsNMe)], [ZneBuLlyl)], [Zn(IBuLsPy2)], [ZneBuLsPhl)], [Zn(IBuLslml)2], [ZneBuLsPy3)2], [Zn(LsC2N)], [Zn(LsNMe)], [Zn(Llyl)], [Zn(LsPy2)] and [Zn(LsPh1)], via Zn(II) templated Schiff- base condensation reactions using two thiosalicylaldehyde derived units and a range of primary amines. The syntheses of 2,4-di-tert-butyl-thiosalicylaldehyde from tert- butyl benzene and three functionalised 1,3-propyldiamines (2-(2-pyridylmethyl)-1,3- propanediamine, 2-(2-pyridylethyl)-I,3-propanediamine and 2-benzyl-I,3- propanediamine) are described. X-ray crystallographic studies demonstrate the successful integration of the additional N-donors into the backbone of the ligand framework at the N-imine position. The range of S2N2, S2N3 and S2N4 ligand sets are shown to adopt an array of coordination geometries about the Zn(II) metal centre providing scope for these ligands in tuning the electronic structures of their Ni- containing complexes. Chapter 3 describes the syntheses and X-ray crystallographic, electrochemical and spectroscopic studies of a series of Ni(II) Schiff-base dithiolate complexes, [Ni(IBuLsC3N)], [Ni(IBuLsc2N)], [NieBuLsNMe)], [NieBuLlyl)], [Ni(IBuLly2)], III [Ni(BuLlhl)], [Ni(BuLs1ml)2], [Ni(tBuLly3h]' [Ni(LsPyl)], [Ni(LsPY2)] and [Ni(LsPhl)] obtained via transmetallation from the analogous [Zn(BuLl)] and [Zn(LsR)] complexes described in Chapter 2. The effect that the additional pendant N-donors have upon the redox properties of the individual complexes are considered with respect to reproducing the structural, spectroscopic and functional properties of NiSOD. Particular attention is focussed on the redox properties of [Ni(BuLsPyl)], [Ni(tBuLsPy2)] and [Ni(BuLsPhl)], which together highlight a rare example of the ability of one N-donor group to assume the role of an endogenous donor upon oxidation. The proposed internal rearrangement of the Ni coordination sphere may encourage the formation of a predominantly metal-based SOMO following the oxidation process. Insight upon how this coordination chemistry relates to the chemistry of the active site of Ni SOD is discussed. Chapter 4 reports the electrochemical and spectroscopic characterisation of a range of binuclear [Ni(LsR)Fe(CO)3] and trinuclear [Ni(LsR){Fe(CO)3h] complexes (R = PhI, PyI and Me) synthesised via the reaction of [Ni(tsalen)]-type complexes, [Ni(LsR)], with Fe2(CO)9. X-ray crystallographic studies show that the complexes incorporate biologically relevant structural elements reminiscent of the active site of [NiFe] hydrogenase, including a binuclear Ni(1l2-S)Fe core featuring a ea. 2.9 A Ni- Fe separation. Chapter 5 details the preparation of a series of Zn(II), Ni(lI) and Cu(lI) Schiff-base diphenolate complexes utilising the two novel pentadentate pro-ligands, [H2tBuLo C3N] and [H2tBuLo NMe]. Cyclic voltammetric, spectroelectrochemical and EPR studies show the Zn(lI) and Cu(lI) complexes support two ligand-based oxidation processes, yielding kinetically inert species possessing phenoxyl radical character. Conversely, the paramagnetic Ni(lI) complexes, [Ni(BuLo NMe)] and IV [Ni(tBuLo C3N)], support both metal and ligand-based oxidation chemistry. The chapter concludes by discussing the relative stability of phenoxyl and phenylthiyl radical ligands by comparison with the redox properties of the analogous Schiff-base Zn(II)-dithiolate complexes described in Chapter 2.

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36

Graham, A. "Binuclear and polynuclear metal complexes with bulky ligands." Thesis, University of Edinburgh, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.651687.

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This thesis presents routes to transition metal complexes of pyridonate and carboxylate ligands. Low nuclearity complexes with triphenyl acetate and 1^strow transition metals of the formula [M₄(OMe)₄(O₂CCPh₃)₄(MeOH)₄] (M = Co, Ni or Zn) have been synthesised and mark a change from reactions with other carboxylates which produce linear trinuclear complexes. Molecular modelling studies investigate the close contacts that arise if triphenyl acetate is incorporated into a linear trinuclear compound to establish whether steric interactions are controlling reactivity. High nuclearity complexes with cobalt and nickel have been, made, many of which extend the range of complexes in which the metal atoms form a centred tricapped trigonal prism. These complexes all contain [M₁₀(OH)₆(O₂CCPh₃)₆(xhp)₆]²⁺ (xhp = a pyridone anion substituted at the six position) core with metal atoms capping the triangular faces of the centred prism. A variant on previous trapped trigonal prisms is also presented, in which the cap metal atoms cap the prism edges. In other complexes the metal atoms form new topologies, ranging from hexa- to octanuclear. In some complexes sodium atoms are also incorporated into the polynuclear cages. Reaction conditions for formation of these cages was investigated. Variation of the metal salt from chloride to nitrate influences both the yield of high nuclearity complexes and the timescale over which they are formed. The choice of recrystallisation solvent affects the cage formed. For example. hexanuclear and heterometallic octanuclear cobalt complexes follow identical syntheses except for the recrystallisation solvent. The means by which counterion and recrystallisation solvent influence reactivity is unclear.

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37

Rivers, Christopher John. "Transition metal complexes incorporating trialkylsilyl substituted pentalene ligands." Thesis, University of Sussex, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.289228.

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38

Harriott, Patrick. "Pendant-arm macrocyclic ligands and their metal complexes." Thesis, Queen's University Belfast, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.336108.

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39

Herring, A. M. "New transition metal complexes containing functionalised phosphine ligands." Thesis, University of Leeds, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.383967.

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40

Khandelwal, B. "Metal complexes of electron-rich arsenic-sulphur ligands." Thesis, University of Exeter, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.378245.

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41

Rahoo, Haji. "Fluxional characteristics of metal complexes of sulphur ligands." Thesis, University of Exeter, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.280893.

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42

Wood, Andrew John. "Mixed-metal complexes incorporating redox-active cyanomanganese ligands." Thesis, University of Bristol, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.311404.

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43

Greatorex, Sam. "Metal complexes of dioxolene and iminonitroxyl radical ligands." Thesis, University of Leeds, 2018. http://etheses.whiterose.ac.uk/21946/.

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This thesis focuses on the design, synthesis and analysis of multinuclear mixed-valent dioxolene complexes and Cu(II) nitroxyl complexes. Chapter 1 contains a review of the relevant literature for the field of mixed-valent dioxolene complexes and molecular magnetism in nitroxyl complexes. Chapter 2 reports the synthesis and crystallographic analysis of a series of novel highly porous solvent-supported supramolecular assemblies of triptycene derivatives. Chapter 3 reports the complexation and characterisation of triptycene derivatives and related multi-dioxolene ligands with Pt(II). Chapter 4 reports the synthesis, complexation and characterisation of a rigid tris(dioxolene) CTC derivative with Pt(II). It also describes the attempted synthesis of coordination polymers containing multi-dioxolene ligands. Chapter 5 reports the synthesis and characterisation of a series of Cu(II) complexes containing the biradical ligand bisimpy. Chapter 6 contains a description of all synthetic procedures undertaken during this work.

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44

Bell, Michael Niall. "Organometallic platinum group metal complexes incorporating macrocyclic ligands." Thesis, University of Edinburgh, 1987. http://hdl.handle.net/1842/13895.

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45

Graham, Alasdair. "Dinuclear and polynuclear metal complexes with bulky ligands." Thesis, University of Edinburgh, 2001. http://hdl.handle.net/1842/12051.

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46

Ivison, Peter. "Transition metal complexes of hard-soft donor ligands." Thesis, Kingston University, 1992. http://eprints.kingston.ac.uk/20562/.

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Chiu, Winnie Wai Hang. "Metal complexes with sulfur and selenium donor ligands /." View abstract or full-text, 2009. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202009%20CHIU.

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Wu, Peng, and 武鹏. "Biomolecules sensing and anti-cancer studies of luminescent platinum (II) complexes with tridentate and tetradentate ligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2009. http://hub.hku.hk/bib/B42664639.

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49

Wu, Peng. "Biomolecules sensing and anti-cancer studies of luminescent platinum (II) complexes with tridentate and tetradentate ligands." Click to view the E-thesis via HKUTO, 2009. http://sunzi.lib.hku.hk/hkuto/record/B42664639.

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Ho, Kin-ying. "Synthesis, characterization and spectroscopic properties of d6 and d10 metal complexes with pyridyl amine ligands /." Hong Kong : University of Hong Kong, 1999. http://sunzi.lib.hku.hk/hkuto/record.jsp?B20667905.

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Dissertations / Theses on the topic 'Tridentate Ligands - Metal Complexes'

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