A series of group 4 metal-carboryne complexes were synthesized by the reaction of Li2C2B10H10 with dichloro group 4 metal complexes. Reaction of (eta2-C 2B10H10)ZrCl2(THF)3 with 2 equiv of [MeC(NCy)2]Li or [nPr 2NC(NPri)2]Li also effectively yielded the corresponding group-4-metal-carboryne complexes. On the other hand, treatment of C2B10H10)ZrCl2(THF) 3 with 2 equiv of tBuOK or [ tBuCOCHCOtBu]Na gave unexpected product [(eta2-C2B10H10) 2Zr(OtBu)(THF)] [Zr(OBu t)3(THF)3] or [sigma:sigma:sigma-{ tBuC(O)=CHC(tBu)(O)C 2B10H10}]Zr(eta2- tBuCOCHCOBut)(THF)2 . / Finally, the reactivities of aforementioned zirconacyclopentene and zirconacyclopentane complexes were studied. A new class of benzocarboranes and dihydrobenzocarboranes were prepared by indirect [2+2+2] cycloaddition of carboryne with two different alkynes, or with one alkene and one alkyne, mediated by Ni(II) or Fe(III). In the presence of CuCl and HMPA, zirconacyclopentenes or zirconacyclopentanes reacted with ortho-dihalobenzene reagents to generate naphthalocarborane or dihydronaphthalocarborane derivatives. A series of carborane fused cyclobutenes and cyclobutane were also prepared from zirconacyclopentenes or zirconacyclopentanes complexes mediated by Cu(II). / Next, the reactivities of Cp2Zr(mu-Cl)(mu-C2B 10H10)Li(OEt2)2 toward alkynes, alkenes and pyridines were studied. Various kinds of internal alkynes, and terminal alkenes reacted with this Zr-carboryne precursor to effectively generate the mono- insertion products zirconacyclopentene and zirconacyclopentane, respectively. Interaction of Cp2Zr(mu-Cl)(mu-C2B10H 10)Li(OEt2)2 and pyridines afforded a new kind of carboranyl zirconocene complexes via C-H activation at alpha-position of pyridines. / Subsequently, the reactivities of group 4 metal-carbroyne complexes toward unsaturated molecules were studied. Polar molecules such as azide, ketone, nitrile, carbodiimide, isocyanate, thioisocyanate, carbon disulfide, and isonitrile were inserted into the M-C bond in metal-carboryne complexes to form mono-, di-, or tri-insertion products. These metal-carboryne complexes, however, showed no reactivity toward internal alkynes and alkenes. Terminal alkynes protonated the carboryne complexes to afford neutral o-carborane. / Ren, Shikuo. / Adviser: Zuowei Xie. / Source: Dissertation Abstracts International, Volume: 72-04, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 250-271). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. Ann Arbor, MI : ProQuest Information and Learning Company, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

No description available.

L'objectif de ce travail est la synthèse de nouvelles familles de molécules inhibitrices de corrosion des métaux, et en particulier de l'acier, et l'évaluation de leur pouvoir inhibiteur. Certaines de ces molécules étant potentiellement chélatantes, la synthèse et l'étude structurale de nouveaux complexes de coordination ont été réalisées. L'originalité du travail réside dans la préoccupation de synthétiser des produits dénués de toxicité par des méthodes de synthèse originales faisant notamment appel aux techniques d'irradiation par micro-ondes. Les molécules organiques utilisées sont des hétérocycles pentaatomiques substitués par des groupements aromatiques riches en électrons ou par des groupements carbonylés aisément transformable en fonctions chélatantes (oximes, imines ... ) et pouvant conduire à des macrocycles. Des procédures de synthèse simples, permettant l'obtention de ces produits avec d'excellents rendements ont été mises au point. Les mesures d'efficacité de ces molécules en tant qu'inhibiteurs de corrosion sont effectuées par Spectroscopie d'Impédance Electrochimique. Dans chaque cas, l'influence du substituant est étudiée, par exemple, pour le groupement pyridyle, la position de l'atome d'azote est discutée. Outre les propriétés inhibitrices de corrosion, Certains dérivés de ces molécules azotés à cinq chaînons tels que les oxadiazoles et pyrazoles présentent l'avantage d'être des ligands potentiellement chélatants et permettent d'obtenir des complexes mono, bi et polymétalliques. Des interactions entre métaux porteurs de spin peuvent s'effectuer par l'intermédiaire de ces ligands assembleurs. / The aim of this work is the synthesis of new families of inhibitory of corrosion molecules of metals, in particular of steel, and the assessment of their inhibitory power. Some of these molecules being potentially chelatants, the synthesis and the structural survey of new complexes of coordination have been achieved. The originality of work resides in the preoccupation to synthesize products deprived of toxicity by original methods of synthesis making notably calI to the techniques of irradiation by microwave. The used organic molecules are heterocyclic compounds substituted by aromatic groupings rich in electrons or by groupings carbonyls comfortably transformable in chelatants functions (oximes, imines ... ) and capable to drive to macrocycles. The simple procedures of synthesis, permit to obtain these products with excellent outputs has been finalized. The measures of efficiency of these molecules as inhibitors of corrosion are done by Electrochemical impedance Spectroscopy. ln every case, the influence of substituting was studied, for example, for the grouping pyridyl, the position of the nitrogen atom is discussed. Besides the inhibitory properties of corrosion, Sorne derivatives of these nitrogenous molecules to five linkages as the oxadiazoles and pyrazoles present the advantage to be potentially ligands chelatants and permit to get the complex mono, bi and polymétallic. Interactions between metals carriers of spin can take lace through the intermediary of these Iigands collectors

Wong, Fai George. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references. / Abstracts in English and Chinese. / Abstract --- p.iii / 摘要 --- p.v / Acknowledgment --- p.vii / Table of Contents --- p.ix / Abbreviations --- p.xiii / Selected List of Tables --- p.xv / List of Compounds --- p.xvi / Chapter Chapter 1 --- Introduction on Metal Amides / Chapter 1.1 --- General Background --- p.1 / Chapter 1.2 --- A General Classification of A/-anionic Ligands --- p.1 / Chapter 1.3 --- Development of Late Transition Metal Amides --- p.3 / Chapter 1.3.1 --- The First Reported Metal Amides from Each Major Block of the eriodic Table --- p.4 / Chapter 1.3.2 --- Metal Amides Supported by the Simple [N(SiMe3)2]- Ligand --- p.4 / Chapter 1.3.3 --- From Simple to Bulkier Silylamido Ligands --- p.6 / Chapter 1.3.4 --- Metal Complexes Supported by Borylamido Ligands --- p.7 / Chapter 1.3.5 --- Metal Complexes Supported by Arylamido Ligands --- p.9 / Chapter 1.3.6 --- Metal Complexes Supported by erfluorinated Arylamido Ligands --- p.10 / Chapter 1.4 --- Objectives of This Work --- p.11 / Chapter 1.5 --- References for Chapter 1 --- p.13 / Chapter Chapter 2 --- Ligand Substitution Reactions of Divalent Late Transition Metal Amides / Chapter 2.1 --- General Background --- p.17 / Chapter 2.2 --- Objectives of This Work --- p.19 / Chapter 2.3 --- Results and Discussion --- p.20 / Chapter 2.3.1 --- Previous Work in Our Group --- p.20 / Chapter 2.3.2 --- Synthesis of Metal Complexes --- p.20 / Chapter 2.3.3 --- Molecular Structure of the Fe(ll) Complex 11 --- p.22 / Chapter 2.3.4 --- Preparation of Mixed Amide-Alkyl Complexes --- p.24 / Chapter 2.3.5 --- Molecular Structures of the Methyl Complexes 12-15 --- p.29 / Chapter 2.3.6 --- Attempts to repare Mixed Amide-Alkoxide Complexes --- p.39 / Chapter 2.3.7 --- Reactivity of the [Co(L2)Me(tmeda)] Complex (17) --- p.39 / Chapter 2.3.8 --- Molecular Structure of the Co(ll) Iodide Complex 18 --- p.43 / Chapter 2.4 --- Summary --- p.45 / Chapter 2.5 --- Experimental Section for Chapter 2 --- p.48 / Chapter 2.6 --- References for Chapter 2 --- p.51 / Chapter Chapter 3 --- Reduction Chemistry of Divalent Late Transition Metal Amides / Chapter 3.1 --- General Background --- p.54 / Chapter 3.2 --- Objectives of This Work --- p.57 / Chapter 3.3 --- Results and Discussion --- p.57 / Chapter 3.3.1 --- Reduction of the Complexes Mn(ll) and Co(ll) Complexes 7 and 9 --- p.57 / Chapter 3.3.2 --- Attempted Synthesis of the Mononuclear Co(l) Complex --- p.59 / Chapter 3.3.3 --- Molecular Structures of the Complexes 19 and 20 --- p.61 / Chapter 3.3.4 --- Reactivity of the Univalent Co(l) Complex [Co(L2)]2 (20) --- p.65 / Chapter 3.4 --- Summary --- p.67 / Chapter 3.5 --- Experimental Section for Chapter 3 --- p.68 / Chapter 3.6 --- References for Chapter 3 --- p.69 / Chapter Chapter 4 --- A reliminary Study on the Coordination Chemistry of erfluorinated Late Transition Metal Amides / Chapter 4.1 --- General Background --- p.71 / Chapter 4.2 --- Objectives of This Work --- p.73 / Chapter 4.3 --- Results and Discussion --- p.73 / Chapter 4.3.1 --- Synthesis of the Ligand recursor[HN(SiMe3)(C6F5)] (21) --- p.73 / Chapter 4.3.2 --- Synthesis of the Lithium Reagent [Li(L3)tmeda]] (22) --- p.74 / Chapter 4.3.3 --- Synthesis of the Fe(ll) and Co(ll) Complexes of the L3 Ligand --- p.75 / Chapter 4.3.4 --- Molecular Structures of the Chloride Complexes 23 and 24 --- p.77 / Chapter 4.4 --- Summary --- p.82 / Chapter 4.5 --- Experimental Section for Chapter 4 --- p.83 / Chapter 4.6 --- References for Chapter 4 --- p.85 / "Appendix 1 General rocedures, hysical Measurements, and X-Ray Structure Analysis" --- p.87 / Appendix 2 Selected Crystallographic Data --- p.89 / Appendix 3 NMR Spectra of Compounds --- p.94

archives@tulane.edu / Metalloenzymes containing copper or molybdenum have attracted considerable attention during the past several decades, as they play significant roles in a variety of biological and chemical areas. In those enzymes, their active sites exhibit unique structural features for fundamental studies in coordination chemistry and for applications in various catalytic reactions. The work described in this dissertation focuses on systematic syntheses of organometallic complexes for use in enzymatic systems as nitrous-oxide reductases (N2OR), acetyl-CoA (acetyl coenzyme A) synthases, or carbon monoxide dehydrogenases (ACS/CODH). Synthesis of diaminobisthiolate (N2S2) ligands with phenyl-connected sulfur and nitrogen atoms are introduced in Chapter 1. The importance of the N2S2 donor atoms in functionalizing the overall enzyme active sites are discussed in Chapter 1. Compared to the previously reported procedures, the new routes in this work allow for improved synthetic control, resulting in enhanced synthetic yields under mild reaction conditions. In Chapter 2, we focus on the synthesis, characterizations and applications of Ni(N2S2) complexes. We start with a new Ni complex with a tetradentate diaminobisthiolate ligand which is a continuation of one of the focuses in the previous chapter. The differences between the new Ni(N2S2) complex and other previously reported complexes with similar structures are discussed. We use both theoretical method (density functional theory calculation) and electrochemical measurements to explore the structural-property characteristics of those complexes. Chapter 3 details the synthesis of several multi-copper clusters for assembling in CuZ active-site analogues for nitrous oxide reduction. In those complexes, tetradentate diaminobisthiolate (N2S2) is used as a backbone ligand. Those complexes exhibit unique redox features due to the mixed valence of the CuI/CuII couple. Their structures are characterized by detailed X-ray crystallography measurements. In chapter 4, we extend the studies in synthesizing analogues in molybdenum- dependent carbon monoxide dehydrogenases (Mo-CODH) active site. Two different synthetic routes are explored to yield a number of Mo- and Cu-based complexes. Electrochemical characterizations are used to investigate the redox features of those complexes. / 1 / bo Wang

New cycloaurated complexes have been synthesised and characterised. The biological and catalytic activity (in the addition of 2-methylfuran to methyl vinyl ketone) of selected complexes was evaluated. New complexes reported in this thesis where fully characterised by NMR (¹H, ¹³C and ³¹P when appropriate) and IR spectroscopy, ESI-mass spectrometry and elemental analysis. The simple cycloaurated iminophosphoranes (2-AuCl₂C₆H₄)Ph₂P=N-R (R = (R,S)-CHMePh, (S)-CHMePh, p-C₆H₄F or But) were synthesised by the reaction of the appropriate ortho-mercurated compound with [Me₄N][AuCl₄] and [Me₄N]Cl in acetonitrile; the complex (2-AuCl₂C₆H₄)Ph₂P=N-(S)-CHMePh was structurally characterised. The cis chloride ligands on the complexes were replaced by chelating dianionic ligands such as thiosalicylate and catecholate - the resulting bis-metallacyclic complexes have a better anti-tumour activity (against P388 murine leukemia cells) than the parent dichlorides. The nitrogen-gold coordinate bond is relatively robust and is not cleaved by cyanide or dithiocarbamate ligands. The reaction of (2-AuCl₂C₆H₄)Ph₂P=N-Ph with PPh₃ results in substitution of the chloride ligand trans to the nitrogen (shown by an X-ray crystal structure). Both the endo ((2-AuCl₂C₆H₄)Ph₂P=NC(O)Ph) and exo ((2-AuCl₂C₆H₄)C(O)N=PPh₃) cycloaurated isomers of the stabilised iminophosphorane Ph₃P=NC(O)Ph were synthesised and structurally characterised. Cycloaurated Ph₃P=S and Ph₃P=Se were synthesised by a transmetallation reaction from 2-Hg[(C₆H₄)P(E)Ph₂]₂ (E = S or Se). The synthesis of cycloaurated Ph₃P=O by an analogous method was unsuccessful. PhP(S)(NEt₂)₂ was also cycloaurated via a transmetallation reaction. X-ray crystallography confirmed the sulfur (not the nitrogen) was coordinated to the gold centre. The complexes show a similar stability and reactivity to the C,N cycloaurated species - the cis chloride ligands can be replaced by the chelating thiosalicylate ligand. Again the bis-metallacyclic species showed better biological activity than the parent dichloride. The direct reaction of the 2-pyridyl sulfonamide ligands 2-(C₅H₅N)CH₂NHSO₂R (R = p-tolyl, Ph or Me), 2-(C₅H₅N)CH₂CH₂NHSO₂R (R = p-tolyl or Ph) or 8-(p-tosylamino)quinoline with refluxing aqueous H[AuCl₄] gave N,N' coordinated complexes containing a five- or six-membered cycloaurated ring. The cycloaurated complexes derived from the ligands 2-(C₅H₅N)CH₂NHSO₂Me and 8-(p-tosylamino)quinoline were structurally characterised. The cycloaurated N,N' systems were not as stable as the C,N systems - reaction with reducing agents led to reduction of Au(III) to Au(I) and elemental gold. The 2-pyridine thiocarboxamide ligands 2-(C₅H₅N)C(S)NHR (R= p-tolyl, CH₂Ph, Me, p-C₆H₅OMe) also underwent direct cycloauration upon reaction with H[AuCl₄]. Coordination via the pyridyl nitrogen and sulfur atom was confirmed by an X-ray crystal structure of cycloaurated 2-(C₅H₅N)C(S)NHCH₂Ph. The N,S cycloaurated systems show poor stability in solution and decompose relatively quickly so applications are limited. The ligand with a 2 pyridyl substituent reacted with H[AuCl₄] in a different manner. Instead of cycloauration, the ligand was oxidised and an internal cyclisation occurred to give a 1,2,4-thiadiazolo[2,3-a]pyridinium heterocyclic ring. The reaction of the cycloaurated dichloride complexes (2-benzylpyridine)AuCl₂ and (2-AuCl₂C₆H₄)Ph₂P=N-Ph with the tripodal Kläui ligands (Na[(C₅H₅)Co{P(O)R₂}₃], R = OMe or OEt) and Tl[BF₄] resulted in the formation of cationic gold(III) salts. In the solid state the Kläui ligand is strongly coordinated through two of the three oxygen atoms, and weakly by the third, giving the gold a distorted square pyramidal geometry. In solution there is rapid interchange between the coordinated and non-coordinated oxygen atoms.

[Typescript] / Includes bibliographical references. / 1 v. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1966

The research work presented in this thesis is a consolidated report of experiments aimed at controlling the product selectivity in photochemical reactions. Water soluble hosts such as p-sulfonato calix[n]arenes (n= 6 or 8) and cyclodextrins have been used to solubilize organic molecules in water and to control the product selectivity. These host molecules control the product selectivity by their ability to encapsulate and interact with guest molecules. Furthermore, carrying out reactions in water as solvent is important from green chemistry point of view.

Thesis (Ph. D.)--Ohio State University, 2006. / Full text release at OhioLINK's ETD Center delayed at author's request

Thesis (Ph. D.)--University of Chicago, 1922. / "Private edition, distributed by the University of Chicago libraries." Also available on the Internet. Also issued online.