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1
Hannon, Michael John. "Metal ion control in oligopyridine coordination chemistry." Thesis, University of Cambridge, 1993. https://www.repository.cam.ac.uk/handle/1810/272558.
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Arrowood, Kimberly Ann. "Combining cyclic peptides with metal coordination." Thesis, Atlanta, Ga. : Georgia Institute of Technology, 2009. http://hdl.handle.net/1853/29700.
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Thesis (M.S.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009.Committee Chair: Weck, Marcus; Committee Member: Collard, David; Committee Member: Kubanek, Julia. Part of the SMARTech Electronic Thesis and Dissertation Collection.
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Sze-To, Lap, and 司徒立. "The structural chemistry of coordination compounds containing d-block or f-block metals." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2010. http://hub.hku.hk/bib/B45204470.
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Lin, Xiang. "The supramolecular chemistry of metal-organic coordination oligomers and polymers." Thesis, University of Nottingham, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.416395.
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Quirk, Jeffrey. "Coordination chemistry of selenoether macrocyclic ligands with transition metal ions." Thesis, University of Southampton, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.242624.
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Näslund, Jan. "Solvated trivalent metal ions in solution : a coordination chemistry study /." Uppsala : Swedish University of Agricultural Sciences, 2000. http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&doc_number=009419319&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA.
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Hall, Christopher. "The coordination of alkanes to transition metal fragments." Thesis, University of York, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.331939.
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Parrott, Suzanne J. "The coordination chemistry of hydrazide and diazenide complexes of rhenium." Thesis, University of Essex, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.315728.
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Ogilvie, Stephen Hudson. "Coordination Frameworks: Host-Guest Chemistry and Structural Dynamics." Thesis, The University of Sydney, 2015. http://hdl.handle.net/2123/15897.
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This thesis investigates the host-guest chemistry and structural dynamics in three families of coordination frameworks – Prussian blue analogues (PBAs), zeolitic imidazolate frameworks (ZIFs), and lanthanoid metal-organic frameworks (MOFs). This was primarily achieved using in situ gas-loading neutron powder diffraction (NPD) to examine various guests in the pore space of these materials. Each of these frameworks contain structural motifs that have previously been identified as influential in the uptake of gases. Gas-loaded NPD of the PBA Fe¬3[Co(CN)6]2 revealed two CO2 adsorption sites, both of which interact with the coordinatively-unsaturated Fe(II) sites. A linear relationship was also observed between the material's thermal expansion behaviour when dosed with increasing amounts of CO2, suggesting the potential for controlled thermal expansion properties. NPD analysis of gas-loaded Co(nIm)2-RHO has revealed five adsorption sites each when this material was dosed with CO2 or D2. Host-guest interactions at CO2 and D¬2 adsorption sites are observed to be predominantly driven by electrostatic interactions with the nitro functional group of the 2 nitroimidazolate bridging ligand. Analysis of CO2-loaded NPD data for Co(mIm)2-SOD revealed only a single CO2 adsorption site that accounted for ca. 17% of the total amount of CO2 dosed. This comparison has helped to confirm the necessity of having ligands with strong charge polarisation in order to achieve guest interaction and crystallographic ordering. NPD analysis of gas-loaded Y(btc) has revealed multiple adsorption sites with dosed with CO2, CD4, and O2. These host-guest adsorption sites typically occur between the guest molecule and the carboxylate functional groups of the bridging ligand. Despite the presence of bare metal sites, only the O2 guest is seen to interact weakly. This has been attributed to the contraction in O-Y-O coordination angles upon desolvation of the host material.
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Higginson, Joshua J. "Synthesis and coordination chemistry of ditopic ligands capable of coordinating metal ions and interacting with anions." Thesis, University of Huddersfield, 2015. http://eprints.hud.ac.uk/id/eprint/26444/.
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The aim of this research was to synthesise a series of novel organic multidentate ligands which contain N-donor domains for the coordination of metal ions and amide or amine hydrogen atoms which are capable of interaction with anions. It was envisaged that incorporation of these two binding units would produce a system where the metal ions would control the ability of the ligand to interact with anions or vice versa. Ligand 1 contains a tetradentate N-donor domain formed by a central bipyridine, two thaizole units and two amide units attached in the 4,4’-position of the bipyridine unit. Reaction of this with divalent metal ions results in a mono-nuclear complex where the metal is bound by the N-donor atoms and the amides interact with a variety of anions. Reaction with monovalent metal ions results in the formation of a dinuclear double helicate with the metal again coordinated by the N-donor domains and the anions interacting with the amide hydrogen atoms. This results in a polymeric assembly in the solid state. Ligand 2 contains an identical tetradentate domain comprised of the same N-donor units; however the single amides in the 4,4’-position have been removed and a diamide attached in the 3,3’-position of the bipyridine unit. Reaction of [L2 with divalent cations results in a similar mono-nuclear species. The metal centre is coordinated by the N-donor atoms and one of the acetyl units from two adjoining ligands with the counter ions undergoing interactions with the diamide hydrogen atoms. Coordination of the same ligand with a monovalent cation resulted in a di-nuclear double helicate, each metal centre is fulfilled by the N-donor atoms of the ligand strand and the hydrogen atoms of the diamide units interact with anions. This too results in a polymeric assembly in the solid state. Ligands 3 and 4 contain the iso-structural tetradentate N-donor domain seen in [L1] and [L2] but their functionality in the 3,3’-position differ. Ligand 3 contains a urea group while ligand 4 has a single amide group attatched to an indole unit. Coordination of [L3] and a divalent metal ion results in the formation of a mono-nuclear species with the metal ion bound by the central bipyridine and the N-donor of two thaizole units. Furthermore each of the urea groups in the 3,3’-position undergo favourable interactions with the perchlorate counter ions. A solid state structure of Ligand 4 was only successful with a monovalent cation resulting in the formation of a dinuclear double stranded species. Each metal centre exhibits a distorted trigonal planar geometry through coordination with a pyridine and thiazole ring of one strand and a single thiazole ring of another. The indole and amide of each ligand strand undergo two sets of interactions; anion interactions through the amide and indole hydrogen atoms as well as complementary intermolecular interactions between the indole N···H units of one ligand and the carbonyl C···O units of another complex. Both [L3] and [L4] exhibit long range order through favourable anion-NH interactions however [L4] also displays complimentary indole/acetyl interactions to develop a larger aggregate species. In all these cases the resultant complex is independent upon which anion is used. However, this is not the case with ligand 5. Reaction of [L5] with Cu(BF4)2 or Cu(ClO4)2 gave a dinuclear double helicate with a cleft within the helicate assembly in which an anion is bound. However, reaction of this with half an equivalent of either sulphate (SO4 2-) or dihydrogen phosphate (H2PO4 -) results in the formation of a different dinuclear double helicate whereby the cleft is occupied by either a dihydrogen phosphate or sulphate anion which bridges the metal centres. Further addition of sulphate results in no change of the ESI-MS indicating the dinuclear double helicate persist however addition of one equivalent of di-hydrogen phosphate leads to the formation of a pentanuclear circular helicate. Each metal centre is coordinated by the pyridine and thiazole units of two different ligand strands and a single Cu···O interaction from one of the dihydrogen phosphates. The inclusion of three dihydrogen phosphates into the centre of the assembly as well as a series of phosphate-ligand and phosphate-phosphate interactions leads to the dimerization of the structure with another set of phosphates from a second assembly. Further reaction of this dinuclear species with one equivalent of (Bu4N)NO3 resulted in the formation of a hexanuclear circular meso-helicate (or mesocate). In this structure each Ndonor domain of a thiazole and pyridine ring coordinate two different Cu2+ metal centres. Each metal centre exhibits a distorted octahedral arrangement with two ligand strands completing 4 of its 6 coordination sites, the remaining sites are occupied by two O-donors of a nitrate anion. In addition an amine of each ligand strand points into the centre of the complex creating a cavity capable of hosting two nitrate anions. Ligand 6 is made up of the same bis-bidentate donors as ligand 5 with the addition of a nitrogen atom into the central phenyl spacer. On reaction of [L6] with a divalent metal ion (e.g. Cu(II)) a simple mono-nuclear structure is observed. Although a mono-nuclear assembly is expected, it is interesting that even a simple change in the ligand strand can have a dramatic affect on the self-assembly process. When a central 1,3-phenylene spacer is employed (i.e. [L5]) a dinuclear double helicate is formed, however, when a 1,3-pyridine unit is contained within the ligand strand (i.e. [L6]) a simple mono-nuclear species is produced.
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Hall, Andrew J. "Transition metal ion coordination in hydrophilic polymer membranes." Thesis, Aston University, 1994. http://publications.aston.ac.uk/9746/.
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The research described within this thesis is concerned with the investigation of transition metal ion complexation within hydrophilic copolymer membranes. The membranes are copolymers of 4-methyl-4'-vinyl-2,2'-bipyridine, the 2-hydroxyethyl ester of 4,4'- dicarboxy-2,2'-bipyridine & bis-(5-vinylsalicylidene)ethylenediamine with 2-hydroxyethyl methacrylate. The effect of the polymer matrix on the formation and properties of transition metal iron complexes has been studied, specifically Cr(III) & Fe(II) salts for the bipyridyl- based copolymer membranes and Co(II), Ni(II) & Cu(II) salts for the salenH2- based copolymer membranes. The concomitant effect of complex formation on the properties of the polymer matrix have also been studied, e.g. on mechanical strength. A detailed body of work into the kinetics and thermodynamics for the formation of Cu(II) complexes in the salenH2- based copolymer membranes has been performed. The rate of complex formation is found to be very slow while the value of K for the equilibrium of complex formation is found to be unexpectedly small and shows a slight anion dependence. These phenomena are explained in terms of the effects of the heterogeneous phase provided by the polymer matrix. The transport of Cr(III) ions across uncomplexed and Cr(III)-pre-complexed bipyridyl-based membranes has been studied. In both cases, no Cr(III) coordination occurs within the time-scale of an experiment. Pre-complexation of the membrane does not lead to a change in the rate of permeation of Cr(III) ions. The transport of Co(II), Ni(II) & Cu(II) ions across salenH2- based membranes shows that there is no detectable lag-time in transport of the ions, despite independent evidence that complex formation within the membranes does occur.
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Bachmann, Julien. "Metal-ligand redox interaction in the multielectron chemistry of porphyrinogen coordination compounds." Thesis, Massachusetts Institute of Technology, 2006. http://hdl.handle.net/1721.1/35314.
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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2006.This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.
Vita. Page 257 blank.
Includes bibliographical references.
Metal complexes of the macrocycle porphyrinogen (calix[4]pyrrole) are studied with an emphasis on the redox activity ("non-innocence") of the ligand (Chapter I). Porphyrinogen complexes of spherical, redox-inert metal dications exist in three oxidation states, dianionic, neutral, and dicationic, characterized structurally by zero, one, and two direct bonds between adjacent pyrroles, respectively. All three are isolated on the preparative scale, and interconverted electrochemically (Chapter II). Each carbon-carbon bond functions as a reservoir of two redox equivalents. The neutral oxidation state exhibits an optical intervalence charge transfer transition, characteristic of ligand-based two-electron mixed valency (Chapter III). Dianionic zinc porphyrinogen reacts with carbon dioxide, and neutral zirconium(IV) porphyrinogen with dioxygen. Two zirconium porphyrinogen units can carry a water molecule as an oxo bridging the metals and two protons on the ligands (Chapter IV). Iron porphyrinogen has three available oxidation states, a dianion, a monoanion, and a dication. The interconversion of the latter two is a selective three-electron transformation, preparatively and electrochemically (Chapter V). complex are largely decoupled from each other and can be chosen independently (Chapter IX).
(cont.) Crystallographic analysis shows that both anionic oxidation states contain the reduced ligand, whereas the dicationic state is based on the oxidized ligand (with two C - C bonds). Paramagnetic NMR confirms the structures in solution. Spectroscopies (EPR, Mössbauer) allow the assignment of well-defined individual oxidation and spin states states for the metal within each overall oxidation state of the complex (Chapter VI). The iron porphyrinogen dication is an oxidant based on an iron(II) center; it oxidizes iodide to diiodine (Chapter VII). The cobalt(II) porphyrinogen dianion can take up two protons, then photoreact to yield reduction of at least one proton to a metalbound hydride, as evidenced by infrared spectroscopy (Chapter VIII). Overall, the results afford a picture of metal-porphyrinogens including structure, electronic structure, and reactivity. The ligand supplements the central metal ion by functioning as a multielectron reservoir. Therefore, the (metal-based) coordination and (ligand-based) redox properties of a given porphyrinogen
by Julien Bachmann.
Ph.D.
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Schulte, Thorben Rüdiger. "Metal- and Ligand-Centered Chirality in Square-Planar Coordination Compounds." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2018. http://hdl.handle.net/21.11130/00-1735-0000-0005-126A-0.
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Partridge, Martin Graham. "Activation and coordination of organic ligands by cyclopentadienyl metal complexes." Thesis, University of York, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.304072.
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Atkinson, Nigel Anthony. "Transition metal complexes with sulphur/nitrogen donor macrocycles and related ligands." Thesis, University of Huddersfield, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.290395.
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Rizzuto, Felix. "Allosteric interactions in coordination cages." Thesis, University of Cambridge, 2018. https://www.repository.cam.ac.uk/handle/1810/278963.
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Biomolecular receptors can catalyse reactions, alter their geometry, and inhibit their activity in response to molecules binding around their periphery. Synthetic receptors that can mimic this allosteric binding behaviour extend the potential applications of host-guest chemistry to programmable molecular systems. Modulating the degree and magnitude of interaction between components within these systems enables the design of chemical behaviour akin to biological complexity. With a view to developing artificial guest-binding regulation systems, a series of metal-organic cages capable of both the peripheral and internal encapsulation of guests are presented: octahedra capable of accommodating two guests in different locations simultaneously; cuboctahedral receptors that bind fullerenes with all-or-nothing positive cooperativity and assemble supramolecular entities internally; a heteroleptic triangular prism capable of recognising steroids and enantiopure natural products; and a tetrahedron that binds fullerene clusters. Each of these architectures employs one or more binding site to either: a) template specific products; b) regulate the cooperativity of binding of large anionic guests; c) assemble coordination complexes and interlocked species inside their cavities; d) alter their morphology in well-defined ways; or e) form assemblies with new electronic and electrochemical functionality. In all cases, chemical systems that respond to multiple stimuli simultaneously are explored, and new applications for bringing multiple species into proximity are detailed. The allosteric binding motifs described herein can be extended to sort reaction mixtures, generate specific isomeric forms, stabilise labile species and promote tuneable modes of intermolecular cooperativity.
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Anderson, Carly Elizabeth. "Synthesis of multidentate PNE ligands and their late transition metal coordination chemistry." Thesis, Durham University, 2007. http://etheses.dur.ac.uk/2598/.
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This thesis describes the synthesis of a family of potentially tridentate PNE (E = NMe, О, S, СН(_2), NPh) ligands comprising a six-membered diheteroatomic saturated ring system bearing a pendent phosphine donor arm and studies on their coordination chemistry with a selection of late transition metals. Chapter 1 comprises an overview of the nature of the bonding of phosphine, amine, ether and thioether donors to metals and reviews the dynamic behaviour of saturated heteroatom-containing ring systems in solution. Selected examples of the coordination chemistry and catalytic applications of complexes of Pd, Pt and Rh are given. Chapter 2 details the concise synthesis of variously-substituted diphenylphosphine- bearing PNE ligands, Ph(_2)PCH(_2)CH(_2)N(CH(_2)CH(_2)) (_2)E (E = NMe, 2.4-1; E = о, 2.4-2; E = S, 2.4-3; E = СН(_2), 2.4-4; E = NPh, 2.4-5; E = NCH(_2)CH(_2)PPh(_2), 2.4-7), by reaction of diphenylvinylphosphine with a cyclic secondary amine. The synthesis of both hydrochloride and chalcogen derivatives are also reported. Attempts to synthesise a related family of PNE ligands with amino-substituents at P were unsuccessful. Similar reactions of allyldiphenylphosphine with N-methylpiperazine led to the formation of Ph(_2)PCH(_2)CH(Me)N(CH(_2)CH(_2)) (_2)NMe as a result of base-catalysed isomerisation of the allyl phosphine. The complexation of the PNE ligands with a variety of Pd(II) fragments is detailed in Chapter 3. Reaction with [PdCl(_2) (MeCN) (_2)] affords the [PdCl{k(^3)-PNE}](^+) Сl(^-) salts when E = NMe, O, S and CH(_2), although when E = NPh and NCHzCHjPPha, the expected products were not obtained. A bidentate [PdCİ2{K^-PN(NMe)}] isomer of 3.1-1 was characterised crystallographically although this was indicated not to be representative of the bulk sample, which consisted mainly of the tridentate [PdCl{Kľ^-PNE}] (^+0Cl(^-)isomer. Treatment of 3.1-l with MgSO(_4) affords the unusual [PdCl{k(^3)-PNE}](^+)1/2[Mg(SO(_4))շ.41-1շՕ] complex which was characterised crystallographically. Reaction of 2.4-1 ֊ 2.4-4 with [PdCl(Me)(cod)] and [PdMe(_2)(tmeda)] affords the [PdCl(Me){K(^2)- PN(E)}] and [PdMe(^2){K(^2)-PN(E)}](^+)Cl(_1) complexes, respectively. Chapter 4 describes the coordination chemistry of the PNE ligands with Pt(II) metal fragments. The reaction of 2.4-1 - 2.4-3 with [PtCİ2(cod)] affords the doubly ligated [PtCl{K^-PN(E)} {k'-P(NE)}]^ СГ complexes with both stoichiometric and half molar equivalents of the platinum precursor. Reaction of the PNE ligands with [р\сі{ц-С1}(РЕїз)]2 gives [PtCl(PEt3){K^-PN(E)}] complexes in all cases.The coordination of the PNE ligands with Rh(I) metal centres is detailed in Chapter 5. Reaction of 2.4-1 ― 2.4-4 with [Кіі2{ц-С1}2(00)4] affords the [RhCl(CO){PNE}] complexes in all cases, although when E = NMe and ร, dynamic interconversion between [RhCl(CO){K^-PN(E)}] and [Rh(CO){K^-PNE}]^ Сl(^-) complexes is observed by low temperature NMR spectroscopy. By contrast, no isomerisation is noted when E = О. When E = NPh and NCH2CH2PPh2, the expected products were not obtained. Abstraction of the metal-bound chloride from [RhCl(CO){PNE}] proved successful when E-= NMe and S but this reaction failed to afford the expected product when E = 0， even in MeCN solution. Full experimental data and methods of preparation for the compounds in this thesis are listed in Chapter 6 with supplementary crystallographic data available in the Appendices.
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Bajwa, Somia Ehsan. "Hybrid multidentate phosphine-alkene ligands for transition metal coordination chemistry and catalysis." Thesis, University of York, 2012. http://etheses.whiterose.ac.uk/2633/.
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The development of a new class of phosphine-alkene and thio-phosphine-alkene ligands based on a chalcone ferrocene framework, represents the primary focus of this study. The synthesis and characterisation of novel ligands, ferrochalcone 32 and thio-ferrochalcone 33, are described. The related alkene-phosphine ligands, the Lei ligand 17 and novel thio-Lei ligand 46, are further detailed. The coordination chemistry of four ligands (17, 32, 33 and 46) with various transition metals (Pt, Pd, Cu, Rh and Au) has been investigated in a comprehensive spectroscopis study. Single crystal X-ray analysis has been conducted at suitable junctures within the project. A surprising finding was that some solution-state structures were found to be different when studied in the solid state. The AuI complexes-containing the ligands have been successfully used in 1,5-enyne cycloisomerisation reactions. In addition to the coordination chemistry of the novel ligand systems, some interesting findings emerged For example, AuI complex of Lei ligand 17 and monodbaPHOS 74 undergoes an interesting solid-state [2+2] intramolecular cycloaddition transformation, giving cycloadduct, 72 and 77. An interesting finding includes the presence of impurity in commercially available Pd(OAc)2. Cyclopalladation of papaverine was carried out using pure and impure Pd(OAc)2, which resulted in the identification of novel Pd-dimer complex, 86. The result suggest that nitrite contaminants derive from impurities in Pd(OAc)2, and not from the oxidation of acetonitrile mediated by metallic Pd0, explain the formation of PdII-nitrito cyclopalladated products. Photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex 90 was also observed.
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Ansari, Nasrin. "Coordination properties of aminophosphine with first row transition metal nitrosyl complexes." Thesis, University of Ottawa (Canada), 1994. http://hdl.handle.net/10393/6862.
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The synthesis of the new thermolabile ironnitrosylhydride complex FeH(NO)(CO)(dppf) is reported. (dppf = 1,1$\sp\prime$-bisdiphenyl phosphino-ferrocene). The facile decomposition of FeH(NO)(CO)(dppf) is interpreted in terms of a homolysis of the Fe-H bond and of a nitrosyl transfer reaction. The synthesis of the structurally characterized iron complex Fe(O=PPh$\sb2$(2-Py))$\sb3\sp2\sp+\cdot$2BF$\sb4\sp-$, by the reaction of Fe(NO)$\sb2$(THF)$\sb2\sp+$ with PPh$\sb2$(2-Py) is described. The proposed mechanism for the formation of Fe(O=PPh$\sb2$(2-Py))$\sb3\sp2\sp+\cdot$2BF$\sb4\sp-$ involves a combination of disproportionation and oxygen transfer reactions. This dipositive iron complex is the first example of a first row transition metal chelated by the oxide of diphenyl(2-pyridyl)phosphines. The synthesis and the reactivity of the cobaltdinitrosyl monometallic Co(NO$\sb2$(PPh$\sb2(2$-Py))$\sb2\sp+\cdot$BF$\sb4\sp-$, Co(NO)$\sb2$(Py)$\sb2\sp+\cdot$BF$\sb4\sp-$, Co(NO)$\sb2$(Py)$\sb2\sp+\cdot$BPh$\sb4\sp-$ and bimetallic Co$\sb2$(NO)$\sb3$(PPh$\sb2$(2-Py))$\sb2\sp+$ -BPh$\sb4\sp-$ complexes are reported. The single crystal X-ray diffraction study of Co(NO)$\sb2$(PPh$\sb2$(2-Py))$\sb2\sp+$BF$\sb4\sp-$ shows that the aminophosphine ligands are co-ordinated through their P-donor sites. In solution, Co(NO)$\sb2$(Py)$\sb2\sp+$BF$\sb4\sp-$ was stable whereas, Co(NO)$\sb2$(Py)$\sb2\sp+$BPh$\sb4\sp-$ decomposed rapidly. The structural study of Co(NO)$\sb2$(Py)$\sb2\sp+$BF$\sb4\sp-$ has led to the proposal of a new theoretical model in which the non-bonded repulsions between the NO and L ligands of the M(NO)(L) moieties provide the most influential factor for fixing the value of the (O)N-M-N(O) angle. The structurally characterized Co$\sb2$(NO)$\sb3$(PPh$\sb2$(2-Py))$\sb2\sp+$ -BPh$\sb4\sp-$ complex is the first example of a bimetallic containing two metal-metal bonded first row transition metals with diphenyl(2-pyridyl)phosphine as a bridging ligand. It is also the first example of a Co$\sb2$(NO)$\sb3\sp+$ bimetallic core stabilized by two diphenyl(2-pyridyl)phosphine ligands coordinated by the P and N donor sites of the ligands arranged in a head-to-head fashion.
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O'Connor, Alice. "High pressure studies of metal-organic frameworks and coordination complexes." Thesis, University of Nottingham, 2017. http://eprints.nottingham.ac.uk/40333/.
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High pressure X-ray crystallography is an effective tool for studying the behaviour of systems in the solid state. It is becoming an increasingly popular technique and offers a way to determine and monitor the behaviour of systems, which in some cases is necessary in order for those particular materials to be used in real-world applications. This thesis explores the use of high pressure X-ray crystallography to understand the behaviour of systems such as metal-organic frameworks (Chapters 4and 5) and the coordination complexes, [1,4-C6H4{PPh2(AuCl)}2](Chapter 6) and chloro(4-ethoxycarbonyl-6-phenyl-2,2′-bipyridyl)platinum (Chapter 7). It also describes hydrostatic limit determinations carried out on 4:1 MeOH/EtOH with additional additives such as silicon grease and/or crystals of [PdCl2([9]aneS2O)] to see how the hydrostatic limit might be manipulated by the use of these additives. It has been possible to determine the hydrostatic limit of a possible pressure-transmitting medium, namely RS3000, which showed an increased pressure limit when compared to the hydrostatic limits for other similar media. This thesis therefore covers a wide range of studieshighlighting some of the diversity that this fieldoffers. To betterunderstand the behaviour of the systems studied, several ancillary techniques have been employed including Hirshfeld surface analysis, Raman spectroscopy, UV/visible spectroscopy and theoretical calculations. In all cases these techniques provided useful information which complemented the results of the high pressure X-ray crystallographic studies.
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Martinez, Ortega Maria Eugenia. "Lipid metal organic networks." To access this resource online via ProQuest Dissertations and Theses @ UTEP, 2009. http://0-proquest.umi.com.lib.utep.edu/login?COPT=REJTPTU0YmImSU5UPTAmVkVSPTI=&clientId=2515.
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Fleming, James S. "d'8-metal complexes of 1,8-divinylnaphthalene and 1,2-divinylbenzene." Thesis, University of Bristol, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.385969.
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Rooke, Stephanie Jane. "Transition metal coordination polymers of novel siloxanes bearing N- donor groups." Thesis, Imperial College London, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.271532.
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Custer, Paul D. "Transition Metal Coordination for the Construction of Supramolecular Molecules." University of Akron / OhioLINK, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=akron1226957658.
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Chan, Hoi-shan. "Syntheses, reactivity and coordination chemistry of d10 metal complexes of phosphorus and nitrogen donating polydentate ligands /." Hong Kong : University of Hong Kong, 1999. http://sunzi.lib.hku.hk/hkuto/record.jsp?B2079289X.
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Carter, Timothy Glen 1976. "New supramolecular assemblies of toxic metal coordination complexes." Thesis, University of Oregon, 2010. http://hdl.handle.net/1794/10562.
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xvii, 147 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number.Supramolecular chemistry is a relatively new and exciting field offering chemists simplistic approaches to generating complex assemblies through strategically designed ligands. Much like the many spectacular examples of supramolecular assemblies in nature, so too are chemists able to construct large, elegant assemblies with carefully designed ligands which bind preferentially to target metal ions of choice. An important concept of supramolecular chemistry, often subtle and overlooked, is secondary bonding interactions (SBIs) which in some cases, act as the glue to hold supramolecular assemblies together. This dissertation examines SBIs in a number of systems involving the pnictogen elements of arsenic and antimony as well as aromatic interactions in self-assembled monolayers. The first half of this dissertation is an introduction to the concepts of supramolecular chemistry and secondary bonding interactions and how they are used in the self-assembly process in the Darren Johnson laboratory. Chapter I describes how secondary bonding interactions between arsenic and aryl ring systems and antimony and aryl ring systems assist with the assembly process. Chapter II is a continuation of the discussion of SBIs but focuses on the interactions between arsenic and heteroatoms. The second half of this dissertation will describe work performed in collaboration with Pacific Northwest National Laboratory (PNNL) in Richland, WA. This work was performed under the guidance of Dr. R. Shane Addleman in conjunction with Professor Darren W. Johnson of the University of Oregon. This portion describes novel systems for use in heavy metal ion remediation from natural and unnatural water sources. Chapters III-V describe functionalized mesoporous silica for use in heavy metal uptake from contaminated water sources. Chapter V describes a new technology invented during this internship at PNNL which utilizes weak bonding interactions between aryl ring systems to produce regenerable green materials for toxic metal binding. This work is ongoing in the Darren Johnson lab. This dissertation includes my previously published and co-authored material.
Committee in charge: Michael Haley, Chairperson, Chemistry; Darren Johnson, Member, Chemistry; Shih-Yuan Liu, Member, Chemistry; James Hutchison, Member, Chemistry; Eric Johnson, Outside Member, Biology
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Nayak, Sanjit. "The Use of Coordination Chemistry Principles to Control Aggregation Processes of Metal Ions." [S.l. : s.n.], 2008. http://digbib.ubka.uni-karlsruhe.de/volltexte/1000009969.
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Gibson, Alexander. "Syntheses and studies on transition metal complexes involving phosphine and thioether ligands." Thesis, University of Southampton, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.243147.
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Jones, Peter Leslie. "The synthesis and study of metal complexes of novel functionalised poly(pyrazol-1-yl)borate ligands." Thesis, University of Bristol, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.336874.
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Wan, Chun-wai. "Spectroscopic properties and coordination chemistry of d10 metal complexes with the polypyridyl and naphthyridyl ligands /." Hong Kong : University of Hong Kong, 2000. http://sunzi.lib.hku.hk/hkuto/record.jsp?B22227301.
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陳凱珊 and Hoi-shan Chan. "Syntheses, reactivity and coordination chemistry of d10 metal complexes of phosphorus and nitrogen donating polydentate ligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1999. http://hub.hku.hk/bib/B31220368.
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Lu, Jianjiang. "Crystal engineering of metal-carboxylate based coordination polymers." [Tampa, Fla.] : University of South Florida, 2004. http://purl.fcla.edu/fcla/etd/SFE0000361.
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Otter, Carl A. "The synthesis and coordination chemistry of mixed donor pyridine/phenol and pyridine/sulfonamide ligands." Thesis, University of Bristol, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.246241.
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Kemats, Kyle. "Examining the Gas-Phase Fragmentation of Select Metal ß-diketonate Complexes Using Computational Methods." Youngstown State University / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=ysu1410787738.
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Kaur, Gurpreet. "Structure and reactivity of dinuclear and polynuclear metal complexes." Thesis, University of Canterbury. Chemistry, 2014. http://hdl.handle.net/10092/9945.
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This thesis documents the successful syntheses of six novel 2,2':6',2"-terpyridine-amine based polydentate ligands and a range of mono-, di-, and polynuclear complexes derived from them. The ability of some dinuclear complexes to affect the rate of hydrolysis of the phosphate diester group in the DNA model compound, bis-p-nitrophenyl phosphate (BNPP) has also been explored. Owing to the presence of two potential ligating groups in each polydentate ligand, a number of dinuclear, tetranuclear and serendipitous supramolecular architectures have been produced and characterised during this research.
The polydentate ligands were synthesised by stepwise functionalisation of the progenitor ligand, 4'-(2"'-toluyl)-2,2':6',2"-terpyridine (L2.1), at its ortho methyl position via free radical bromination, and where various amine groups were appended by nucleophilic substitution reactions. The detailed ligand syntheses, and characterisation are discussed in Chapter 2, along with the crystal structures of some ligands.
Chapter 3 describes coordination chemistry of 4'-(2"'-toluyl)-2,2':6',2"-terpyridine with transition metal ions. Thirteen new complexes of Ni(II), Cu(II), Zn(II) and Ag(I) are reported, where Ag(I) produced a striking spiral shaped polymer with L2.1 having unusual „hyperdentate‟ nitrogen atoms.
Two polydentate ligands, 4'-[2"'-{(2-pyridylmethyl)aminomethyl}phenyl]-2,2':6',2"-terpyridine, L2.3, and 4'-[2"'-{bis(2-pyridylmethyl)aminomethyl}phenyl]-2,2':6',2"-terpyridine, L2.4, produced six different dinuclear and tetranuclear metal complexes (Chapter 4).
The Zn(II) dinuclear complexes were used to study kinetics of hydrolysis of BNPP, and the enhanced rates were reported compared to the analogous mononuclear complexes. The detailed experimental methodology and results are discussed in Chapter 5.
The most interesting outcome of this research was formation of the box and wheel shaped complexes, where the ligand L2.3 binds with different metal ions via different coordination modes. The box shaped tetranuclear complexes were synthesised deliberately via structural control over the coordination chemistry of terpyridine-type site of L2.3, where the coordination flexibility of the pendent picolylamine-type site of the ligand was used to bind with other metal ions.
The tetranuclear [M¹₂M²₂(L2.3)₄X₂]⁶⁺ box shaped complexes were formed when two divalent M¹ ions bridge between the ligands to produce octahedral bis-terpyridine type complex M¹(L2.3)₂, and then two divalent M² ions link two M¹(L2.3)₂ units together through picolylamine binding sites, where X = Cl⁻, Br⁻, CH₃COO⁻; M¹ = Fe(II), Zn(II), Ni(II); M² = Zn(II), Cu(II).
The bis-bidentate bridging ligand terephthalate was also deliberately encapsulated in the middle of Fe₂Zn₂L2.3 box to produce the complex where X₂ = terephthalate. These structures invite speculation that it may be possible to bind and react molecules within these boxes.
In a more fortuitous outcome, Ni(II) ions were found to bind to both sites of L2.3 to give, exclusively, an unprecedented decanuclear wheel-shaped structure. A halide ion occupies the central position in the wheel, with Br⁻ being preferred over Cl⁻. The detailed crystal structures, and properties of the wheels shaped Ni₁₀(L2.3)₁₀ complexes are discussed in Chapter 6.
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Boyd, Thomas. "From molecular assemblies to extended frameworks of polyoxometalates through secondary metal ion coordination." Thesis, University of Glasgow, 2013. http://theses.gla.ac.uk/4492/.
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The work detailed in this thesis is presented and discussed in three distinct chapters, which constitute a general and progressive study into polyoxometalate (POM) chemistry. This began with the development of a new synthetic strategy towards a family of transition metal-substituted POMs (TMSPs), continued through the study of POM physical properties in solution, and culminated in the empirical analysis of a new family of structures. During this work, the focus was primarily on crown-type POMs and their function as supramolecular inorganic hosts, both as discrete ‘zero-dimensional’ structures, and as an integral part of porous multi-dimensional frameworks. Four iso-structural triple Wells-Dawson-type phosphotungstate compounds, which incorporate six transition metal (TM) centres are discussed, with two of the compounds presented for the first time. An in-depth comparative study of the structures of the four TMSPs has been conducted, and related back to the synthetic conditions which gave rise to their formation. Electrochemical and electrocatalytic studies of the four compounds are also detailed. Although a great number of TMSPs of various shapes, sizes and composition is already known, the establishment of iso-structural TMSP families is still rare. In the second chapter, the application of isothermal titration calorimetry to assess the binding properties of the crown-type POM, [P8W48O184]40- ({P8W48}), is discussed. To facilitate these studies, {P8W48} was prepared in the absence of potassium to give two new mixed lithium/ammonium salts. Distortion of the {P8W48} ring, previously only observed in compounds with TM substitution, was observed both in solution and in the solid state, whilst this investigation also revealed ‘super-crown’ behaviour of the compound. {P8W48} is also an ideal building block for the construction of inherently-porous framework materials. However, the coordination of 1st-row TMs to this POM ring has so far proven unpredictable, and established compounds are often difficult to reproduce. Comprehensive analysis of {P8W48}-based frameworks was therefore performed to unite a group of previously disparate compounds. This class of inorganic framework materials is termed POMzites due to members’ all-inorganic POM scaffolds, their oxygen-rich and anionic nature, and their micro-scale porosity
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Faustino, Brissos Rosa Maria. "Coordination, organometallic and supramolecular chemistry approaches to the design of metal-based cytotoxic agents." Doctoral thesis, Universitat de Barcelona, 2018. http://hdl.handle.net/10803/544129.
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The discovery of cisplatin and its successful use as chemotherapeutic agent have encouraged the development of metal-based anticancer molecules.
The present doctoral research project includes three different chemistry approaches to design new metal-based cytotoxic compounds. Coordination, organometallic and supramolecular chemistry have been used to successfully develop three families of compounds with highly promising biological properties.
Copper(II) coordination compounds of various nuclearities have been prepared from new Schiff-base ligands. The complexes strongly interact with DNA without cleaving it and exhibit notable cytotoxicities against various murine and human cancer cell lines.
Organometallic ruthenium(II)-arene compounds containing a monophosphane PR3 ligand have been obtained, which show remarkable cytotoxicites against a wide panel of human cancer cells, so as very interesting antimetastatic properties. Structureactivity relationship studies have been carried out, which illustrated the great potential (and versatility) of this family of molecules, whose biological properties can be finetuned by the selection of the different ligands bound to the metal.
A new family of supramolecular compounds has been developed with the objective to target the DNA major groove or/and stabilize non-conventional DNA structures, for instance the three-way junction (3WJ). The series of iron(III) metallohelicates prepared exhibit groove-binding properties but are not capable of stabilizing the 3WJ. Some of these helical complexes show interesting cytotoxic properties and one of them can even induce cell apoptosis.El descobriment que cisplatí és un fàrmac molt útil en quimioteràpia ha encoratjat el desenvolupament de fàrmacs antitumorals basats en metalls. El projecte de recerca d’aquesta Tesi Doctoral inclou tres aproximacions diferents pel disseny de nous compostos citotòxics basats en metalls. Així doncs, tant la química de coordinació com l’organometàl·lica i supramolecular s’han emprat per desenvolupar tres famílies de compostos amb propietats biològiques molt prometedores. S’han preparat complexos de Cu(II) amb imines (bases de Shiff) de diverses nuclearitats. S’ha trobat que els complexos interaccionen fortament amb l’ADN sense escindir-lo i tenen citotoxicitats elevades en diverses línies de cèl·lules canceroses de ratolí i també humanes. S’han estudiat també compostos organometàl·lics de Ru(II) amb fosfines terciàries PR3 i s’ha trobat que són molt citotòxics en un ampli espectre de línies cel·lulars canceroses humanes. A més, presententen un efecte antimetastàtic molt interessant. S’han establert relacions estructura-propietat, fet que il·lustra el gran potencial i versatilitat d’aquesta família de molècules perquè les propietats es poden modular segons el lligand fosfina unit al metall. Finalment, s’ha desenvolupat una nova família de compostos supramoleculars amb l’objectiu que interaccionin amb el solc gran de l’ADN i/o estabilitzar estructures no convencionals de l’ADN com per exemple unions triples (3WJ). Així doncs, s’ha trobat que els metal·lohelicats de Fe(III) que s’han preparat s’uneixen al solc major de l’ADN però no son capaços d’estabilitzar les unions triples 3WJ. Alguns d’aquests compostos presenten propietats citotòxiques interessants i un d’ells fins i tot indueix l’apoptosi cel·lular.
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Marquez, Acuna Victoria Elena. "Coordination chemistry of macrocycles and metal complexes containing a nitrogen and sulphur donor set." Thesis, University of Cambridge, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.279727.
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尹俊偉 and Chun-wai Wan. "Spectroscopic properties and coordination chemistry of d10 metal complexes with the polypyridyl and naphthyridyl ligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2000. http://hub.hku.hk/bib/B31223564.
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Hager, Emma. "The design and synthesis of new transition metal coordination complexes as potential anti-malarial agents." Doctoral thesis, University of Cape Town, 2011. http://hdl.handle.net/11427/10667.
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Pastor, Michael Bernard. "Bimetallic complexes: The fundamental aspects of metal-metal interactions, ligand sterics and application." Scholarly Commons, 2018. https://scholarlycommons.pacific.edu/uop_etds/3559.
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Metal containing complexes have been used to catalyze various organic transformations for the past few decades. The success of several mononuclear catalysts led to transition metal catalysts used in pharmaceuticals, environmental, and industrial processes. While mononuclear complexes have been used extensively, bimetallic systems have received far less attention. Bimetallic or polynuclear sites are commonly found in metalloenzymes that perform elegant transformation in biological systems, underlying their significance. Inorganic chemists take inspiration from nature and design model bimetallic complexes to further study this cooperativity effect. A bimetallic platform offers many structural and functional differences such as the identity of the metal atoms and the bonding interactions between metals, which have been reflected in their unique catalytic ability and reactivity.
This dissertation encompasses work related to the computational study of metal-metal interactions of bimetallic systems, the 1H NMR study of stereochemical and conformational changes in solution of N,Nʹ-diarylformamidines, the synthesis of dizinc formamidinate complexes, and the synthesis and catalytic ability of dicopper formamidinate complexes.
In the first part, DFT calculations are used to study factors that influence metal-metal bond lengths in various complexes. Several experimentally obtained X-ray crystal structures were used as the basis for the study. Differences in metal-metal separations were investigated through various functionals, indicating the importance of charge, orbital interactions, and formal bond order. BH&HLYP SDD/aug-CC-PVDZ geometry optimizations of octahalodimetalate anions Tc2X8n- (X = Cl, Br; n=2, 3), Re2X82- (X = Cl, Br), and Mo2Cl84- reproduced M-M bond distance trends observed experimentally. The study demonstrated that the increase in σ and π bond strength resulted in the shortening in Tc-Tc bond distance from Tc2X82- to Tc2X83-, which was further supported by the short Mo-Mo bond in the Mo2Cl84- ion. This study was expanded further through the inclusion of [M2Cl4(PMe3)4]n+ (M = Tc, Re, n = 0-2) and [Mo2E4]n- (E = HPO4 or SO4, n = 2-4), allowing a systematic study on the role of charge on the metal atoms. PBEO SDD/aug-CC-PVDZ calculations revealed that both formal bond order and formal charge on the metal atoms dictate the trends in M-M bond strength.
The second half of this dissertation focuses on the synthesis and characterization of bimetallic Zn- and Cu-formamidinate complexes. The stereochemical exchange of substituted N,Nʹ-diarylformamidines were studied through 1H NMR in various solvents. Alkyl substituents placed on the ortho positions were found to shift the isomeric equilibrium in solution through destabilization of the hydrogen-bond dimer evident in X-ray crystal structures. The Z-isomer of substituted N,Nʹ-diarylformamidines is observed in CDCl3, C6D6, and DMSO-d6 when the ligands feature significant steric hinderance. Similar ortho substituted N,Nʹ-diarylformamidines were also used to enforce steric interactions to limit the nuclearity of Zn-formamidinate complexes. Various dizinc formamidinate complexes were synthesized through direct and transmetalation routes. NMR and mass spectrometry were used alongside X-ray crystal structures to fully characterize the dizinc complexes. Dicopper formamidinates formed through a transmetallation route were synthesized and feature distinct short Cu…Cu separations thought to be brought about by metalophillic interactions. Preliminary results suggest catalytic ability of dicopper formamidinates in cyclopropanation and aziridination of styrene with various diazo compounds. The catalytic activity suggests the formation of dicopper carbene and nitrene intermediates, of which only few published experimentally observed examples exist in the literature.
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Hewson, Sean. "Active metal template synthesis of [2]rotaxanes." Thesis, Queensland University of Technology, 2021. https://eprints.qut.edu.au/212366/1/Sean_Hewson_Thesis.pdf.
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This thesis describes the use of metals to simultaneously catalyse and template large molecules into a mechanically interlocked system. This mechanical interlocking results in unique properties but is difficult to achieve. In this thesis, techniques to create this mechanical interlocking are developed and improved upon both in solution and on surfaces. In addition, the complex molecules that are created display unique properties and this behaviour is analysed in depth.
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Hashiguchi, Ryota. "Studies on Polynuclear Metal Complexes and Low-Dimensional Mixed-Valence Halogen-Bridged Transition Metal Complexes Based on them." 京都大学 (Kyoto University), 2017. http://hdl.handle.net/2433/225426.
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Olson, Justine Rose. "Early transition metal and actinide coordination chemistry of a bicyclic guanidinate ligand: synthesis, characterization, and luminescence." Diss., University of Iowa, 2017. https://ir.uiowa.edu/etd/5588.
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The bicyclic guanidinate 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate (hpp–) has been recognized as an excellent stabilizing ligand for low oxidation state metals for about a decade. It has been used as a dinucleating anionic ligand in the synthesis of complexes containing the ‘paddlewheel’ structure motif (which often contain metal-metal multiple bonds) and is resistant to reductive cleavage by low-valent metal centers. One drawback to the ligand is that its metal complexes often have reduced solubility. This can be problematic in isolation and characterization. One solution to this problem is alkylation of the rings. Two derivatives of hpp–, tetramethyl-hppH (hpp*H) and tetraethyl-hppH (hpp”H) have published syntheses that were irreproducible by our research group.
New and easily reproducible syntheses for hpp*H and hpp”H are presented. The syntheses of (hpp*)SiMe3 and (hpp”)SiMe3, which are liquid silanes that can be isolated and purified for better stoichiometric control when transferring hpp–, hpp*–, and hpp” – onto metal centers, are also described. Chapter 3 details the synthesis of several high-valent mononuclear tantalum and zirconium complexes containing hpp– and hpp*– using these silanes. The solid-state structures of the Ta(hpp*) compounds are compared to those of the previously reported Ta(hpp) compounds.
In the course of this research, it was discovered that the M(hpp)/M(hpp*) [M = Zr, Ta] complexes were highly fluorescent, exhibiting intense Ligand-to-Metal Charge Transfer (LMCT). A series of Zr(hpp)(bpy) [bpy = 2,2’-bipyridine] complexes containing different bpy derivatives were synthesized to explore the possibility of Ligand-to-Ligand Charge Transfer, a very rare phenomenon for zirconium, and are also detailed in chapter 3. Chapter 4 describes the spectrofluorimetry of the synthesized Ta(hpp), Ta(hpp*), Zr(hpp), and Zr(hpp)(bpy) complexes.
Since hpp*– is known to change electronics at the metal center compared to hpp–, we wanted to investigate if its effects could be examined by spectroscopy. Chapter 5 describes the synthesis of several metal-oxo hpp complexes that were characterized via the M=O IR stretch. The comparison was made between MO(hpp)2L and MO(hpp*)2L [M = W, Re]. The M=O IR stretches were verified by 18O isotopic labeling. Attempts at synthesizing TaOCl3 and TaO(hpp)2L are also detailed.
In the last chapter (chapter 6), a few U(hpp) complexes were generated during our development of non-cyclopentadienyl hpp– coordination chemistry of uranium, and are discussed. Two of the complexes characterized via X-ray crystallography are diuranium complexes with UIV-UIV distances of 3.56 Å, possibly being the first compounds with U-U bonds. The new complex U(hpp*)4 is also described.
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Cetin, Anil. "TRANSITION METAL COMPLEXES OF PORPHYRIN ANALOGS AND BORATE-BASED COORDINATION COMPLEXES." University of Akron / OhioLINK, 2007. http://rave.ohiolink.edu/etdc/view?acc_num=akron1176390111.
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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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Collins, David J. "Synthesis of Heterobimetallic Clusters and Coordination Networks via Hard-Soft Interactions." Miami University / OhioLINK, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=miami1209484624.
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Clough, Benjamin. "New scandium and titanium borylimido chemistry." Thesis, University of Oxford, 2017. https://ora.ox.ac.uk/objects/uuid:1a9dbfb3-98c3-4fd6-96ac-5fba09f3ffcd.
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This Thesis reports the synthesis and reactivity of scandium and titanium borylimides. New, versatile synthetic routes to such complexes of these two metals were targeted, and their reactions with small, unsaturated compounds were explored, with a particular focus being the reactivity of alkynes with these systems. Chapter One provides a background on Group 4 imido and hydrazido complexes. Group 4 alkoxyimides are also reviewed, as well as the developing field of rare earth imides. The Chapter focuses on the synthesis, structure, and stoichiometric and catalytic reactions of these complexes with unsaturated substrates, and ends with a description of the handful of known transition metal borylimides. Chapter Two first describes the synthesis and structures of new titanium borylimido synthons prepared from Ti(NMe2)2Cl2. From the borylimide Ti{NB(NAr'CH)2}Cl2(py)3 are then formed five new compounds supported by a range of tridentate, nitrogen-based ligands. Chapter Three describes the synthesis of half-sandwich titanium borylimides through tertbutylimide/borylamine exchange. A sandwich compound is also described, and the electronic structures of these complexes are analysed by DFT, QTAIM and NBO studies. Reactivity with heteroallenes, and exchange reactions with amines are also explored. Chapter Four describes the reactivity of diamide-donor-supported titanium borylimides with terminal alkynes. The principal reaction outcomes are [2+2] cycloadditions and CâH bond activations, and an interesting CâF bond activation is also described. Kinetic studies of some reactions are presented, and will be supported by further DFT studies. Chapter Five explores attempts to prepare the first rare earth borylimide. Kinetic and computational evidence is presented for the existence of a transient scandium borylimide which rapidly undergoes interesting sp, sp2 and sp3 CâH bond activations. Chapter Six presents full experimental procedures and characterising data for the new complexes reported.
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Mouttaki, Hasnaa. "Quest toward the Design and Synthesis of Functional Metal-Organic Materials (MOMs): A Supermolecular Building Layer Approach (SBL)." Scholar Commons, 2015. https://scholarcommons.usf.edu/etd/5540.
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Metal-Organic Materials (MOMs) represent an important division of coordination chemistry. They are self-assembled through the linking of metals with organic ligands. They gained their spotlight among scientists for their aptitude for design and facile synthesis via their multi-component coordination, and their readiness to functionalization. MOMs have been targeted for specific industrial and environmental applications such as gas storage, catalysis and CO2 sequestration.
Throughout the past decade, studies have been conducted to develop systematic approaches toward the design and synthesis of functional MOMs. Their synthesis from targeted building units has facilitated their rational design and functionalization. The Molecular Building Block (MBB) approach was first developed to direct the design of MOMs from preset building blocks with specific connectivity amenable to form the overall MOM structure with the desired topology. These building blocks are easily constructed in situ through the chelation of multifunctional ligands (i.e, carboxylic acid, amine, etc) to single ion or cluster metals such as dinuclear copper paddlewheel, and basic zinc acetate. As complexity and applications for MOMs increased, a new approach was developed through the utilization of Supermolecular Building Blocks (SBBs) for the assembly of more complex and higher connected MOM structures. The SBB approach is implemented through the formation of highly coordinated metal-organic polyhedra (i.e, small rhombihexahedron, cuboctahedron, etc) which are further linked by organic ligands to construct functional porous materials with the desired net topology.
In this work, we focus on the implementation of a new design approach based on utilizing targeted [M(R-BDC)]n 2D layers as building blocks, i.e Supermolecular Building Layers (SBLs). We target well-known 2D layers that are amenable to pillaring through organic building blocks with specific geometries (i.e quadrangular, hexangular) in order to rationally design and synthesize functional porous metal-organic materials. These SBLs are derived from multifunctional ligands capable of both directing the formation of the 2D layers and pillaring to construct the overall targeted 3D structures with the desired topology (i.e, tbo-MOMs, eed-MOMs, mmm-MOMs, bor-MOMs, and eef-MOMs). Ultimately, we construct isostructural, and isoreticular materials which show potential for many applications such as gas storage, gas separation, and catalysis. These materials have been targeted through the rational choice of specific ligands and proper metals which we recognized to have the capability and the functionality to direct the construction of the desired functional materials and to reach our research goals.
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Moleko, Pulleng. "The coordination and extractive chemistry of the later 3d transition metal ions with N, N'-donor imidazole-based ligands." Thesis, Nelson Mandela Metropolitan University, 2014. http://hdl.handle.net/10948/8382.
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The application of bidentate N,N'-donor ligands, such as 2,2'-biimidazole (BIIMH2) and 2,2'-pyridylimidazole (PIMH) and (1H-benzimidazol-2yl)-N-methylmethanamine (BIMAH), in the solvent extraction of base metal ions from an acidic sulfate/sulfonate medium was investigated. PIMH and BIMAH showed selectivity for Ni(II) with the only interfering ion being Cu(II) in the pH range 1.2-1.8 but BIIMH2 lacked selectivity. The extraction patterns observed were influenced by stereochemical aspects, and this agreed well with the envisaged design of nickel(II)-specific extractants through stereochemical “tailor-making” which is proposed in this study. The extraction patterns were explained from a coordination chemistry point of view using spectroscopic analysis and single crystal X-ray analysis to diagnose the geometry of the complexes formed from the interaction of the base metal ions with the ligands. The formation of the trigonal bipyrimidal [Cu(PIM)2(H2O)](SO4) complex, with a water molecule coordinated, while nickel(II) forms a square planar bisPIMH was put forward as the reason for extraction pattern observed with this ligand. Cobalt(II) also forms a bisPIMH complex but has two water molecules coordinated in the formation of a distorted octahedral complex, and this results in less extractable species. A similar observation as for PIMH was noticed in BIMAH complexation reactions. The BIIMH2 complexes were found to be distorted octahedral, through the bis-coordination of BIIMH2 and two sulfonate ions, resulting in lack of pH-metric separation of the later 3d metal ions. The stability constants data was in agreement with what was observed in the solvent extraction and coordination chemistry studies for the three ligand systems.