Tesi: "Metal carbonyl compounds"

1

Taylor, Paul H. "Metal free-oxygenation of carbonyl compounds". Thesis, Cardiff University, 2010. http://orca.cf.ac.uk/54244/.

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Abstract (sommario):

The findings to date have contributed to the development of a novel and useful class of synthetic protocol and have resulted in a greatly enhanced understanding of the fundamental workings of the &agr;-oxygenation.

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2

Bojczuk, M. "Carbonyl exhange mechanisms in transition metal compounds". Thesis, University of Kent, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.372765.

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3

Lorusso, Patrizia. "Metal catalysed alkylation of carbonyl compounds with formaldehyde". Thesis, University of St Andrews, 2015. http://hdl.handle.net/10023/7823.

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Abstract (sommario):

Formaldehyde is a chemical used widely in the manufacture of building materials. A remarkable example is represented by the Lucite two-step Alpha technology for the large scale production of methyl methacrylate (MMA), the essential building block of all acrylic-based products. Esters and ketones are important intermediates in the manufacture of acrylate esters therefore α-hydroxymethylenation of carbonyl compounds using formaldehyde as a one carbon alkylating agent and subsequent dehydration to the corresponding methylenated derivatives has been explored in the current work. We report a novel catalytic approach for the synthesis of methyl methacrylate (MMA) via one-pot α-methylenation of methyl propanoate (a chemical intermediate of the ALPHA process) with formaldehyde, generated in situ by Ru-catalysed dehydrogenation of methanol. Elucidation of the mechanism involved in the catalytic dehydrogenation of methanol along with the collateral alcohol decarbonylation reaction was gained through a combined experimental and DFT study. The development of an alternative process where anhydrous formaldehyde is produced in situ would provide a simplification over the current second step of the ALPHA technology where the formaldehyde is initially produced as formalin, subsequently dehydrated to afford anhydrous formaldehyde in order to ensure high selectivity to MMA. As an alternative approach, ketones, in particular 3-pentanone and 2-butanone, were targeted as potential substrates in order to overcome some of the problems related to competing reactions that occur at the ester group. Hydroxymethylenation, followed by dehydration and Baeyer-Villager oxidation, possibly catalysed by enzymes to reverse the normal selectivity, leads to the formation of acrylate esters. The catalytic reaction is enabled by a gold carbene hydroxide complex in such a way that the substrate undergoes C-H activation and the nascent metal alkyl acts as a nucleophile towards the electrophilic formaldehyde, supplied in the form of alcoform* (solution of paraformaldehyde in methanol).

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4

Llewellyn, Simon. "Acyl carbonyl transition metal compounds : their homologation and hydrogenation". Thesis, University of Oxford, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.433556.

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5

洪若華 e Yeuk-wah Hung. "The chemistry of Osmium-Rhodium mixed-metal carbonyl clusters". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1998. http://hub.hku.hk/bib/B3121535X.

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6

Hung, Yeuk-wah. "The chemistry of Osmium-Rhodium mixed-metal carbonyl clusters /". Hong Kong : University of Hong Kong, 1998. http://sunzi.lib.hku.hk/hkuto/record.jsp?B19904988.

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7

Ladogana, Santino. "Kinetics and Mechanisms of Metal Carbonyls". Thesis, University of North Texas, 1998. https://digital.library.unt.edu/ark:/67531/metadc278709/.

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Abstract (sommario):

Pulsed laser flash photolysis with both visible and infrared detection has been applied to the study of the displacement of weakly coordinating ligands (Lw) by strongly "trapping" nucleophiles (Ls) containing either an olefinic functionality (Ls = 1-hexene, 1-decene, 1-tetradecene) or nitrogen (Ls = acetonitrile, hydrocinnamonitrile) from the photogenerated 16 electron pentacarbonylchromium (0) intermediate. 5-Chloropent-l-ene (Cl-ol), a potentially bidentate ligand, has been shown to form (ol-Cl) pentacarbonylchromium (0), in which Cl-ol is bonded to Cr via a lone pair on the chlorine, and isomerize to (Cl-ol) pentacarbonylchromium (0), in which Cl-ol is bonded to the olefinic functionality on the submillisecond time scale. This process has been studied in both the infrared and visible region employing both fluorobenzene or n-heptane as the "inert" diluent. Parallel studies employing 1-chlorobutane and 1-hexene were also evaluated and showed great similiarity with the Cl-ol system. The data supported a largely dissociative process with a possibility of a small interchange process involving the H's on the alkyl chain. Studies were also carried out for various Cr(CO)6/arene/Ls systems (arene = various alkyl or halogenated substituted benzenes). The data indicated that for both C6H5R (R=various alkyl chains) or multi-alkyl substituted arenes (i.e. o-xylene, 1,2,3-trimethylbenzene) containing an "unhindered" ring-edge, bonding to the the Cr(CO)5 moiety occurs "edge on" via a partially delocalized center of unsaturation on the ring. The data indicated that both electronic and steric properties of the arenes influence the kinetics, and that an interchange pathway takes place at least, in part, through the alkyl chains on both the arenes and "trapping" nucleophiles. Moreover, halogenated arenes bond through the lone pair on the halogen for both CI- and Br- derivatives but "edge-on" for the fluorinated arenes. Finally, in the case of arene complexes without and "unhindered" ring-edge (i.e., 1,2,3,4,5-pentamethylbenzene) bonding can occur either "edge-on" or through the ring center of the arene or combination of the two. Carbonyl stretching frequencies for the arenes are also indicative of the type of bonding.

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8

Mansour, Saber E. (Saber El-Sayed). "The Nature of Intermediates Produced Through Ligand-Substitution Reactions of Octahedral Metal Carbonyls". Thesis, North Texas State University, 1986. https://digital.library.unt.edu/ark:/67531/metadc331634/.

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Abstract (sommario):

Pulsed laser time-resolved ligand-substitution photochemistry for (DTO)W(CO)4, (DTN)W(CO)4, and (NP)Mo(CO)4 (DTO = 2,2,7,7-tetramethyl-3,6-diathiaoctane; DTN = 2,2,8,8- tetramethyl-3,7-diathianonane; NP = l-diethylamino-2- diphenylphosphinoethane) proceeds via initial fission of the W-S and Mo-P bonds, affording Cs and C4v five-coordinate intermediates for DTN and NP but largely Cs for DTO. The rates of reaction of these intermediates, via chelate ring closure and competitive bimolecular interaction with Lewis bases (= L, alkylphosphines and alkyl phosphites) for the Cs intermediates and via bimolecular interaction of L with the C4v intermediates, together with activation parameters for these processes have been determined. The rates of interactions at the Cs intermediates are significantly faster than at the C4v intermediates.

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9

王淑儀 e Shuk-yee Janet Wong. "The chemistry of osmium carbonyl clusters containing oxime and oxo ligands". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2003. http://hub.hku.hk/bib/B31244932.

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10

Ismail, Ashraf A. "Chalcocarbonyl chemistry : application in hormonal receptor determination, metalloporphyrins and metal-arene bond activation". Thesis, McGill University, 1985. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=72063.

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The reaction of ((eta)-Arene)Cr(CO)(,2)(CX) (X = S, Se) complexes with excess (RO)(,3)P (R = Me, Et, n-Bu, Ph) yields Cr(CO)(,2)(CX) (RO)(,3)P (,3), predominantly as the mer I isomer, in which a phosphite ligand is trans to CX. Arene displacement from ((eta)-C(,6)H(,6))Cr(CO)(,2)(CX) by tridentate phosphine ligands L-L-L L-L-L = (Me)C(CH(,2)P(Ph)(,2))(,3), (Ph(,2)PCH(,2)CH(,2))(,2)PhP gives fac-(L-L-L)Cr(CO)(,2)(CX) products. The molecular structures of Cr(CO)(,2)(CX) (MeO)(,3)P (,3) have been determined by single crystal X-ray diffraction. Intramolecular isomerization of these complexes as well as their tricarbonyl analogue has been demonstrated and activation parameters have been calculated for the rearrangement processes. Two-dimensional ('31)P NMR spectroscopy has provided evidence that isomerization occurs via trigonal prismatic intermediates. Kinetic investigations of the reaction of ((eta)-C(,6)H(,6))Cr(CO)(,2)(CX) with (MeO)(,3)P have established a first-order rate dependence on both the complex and the entering ligand. The faster reaction rate of the selenocarbonyl derivative relative to its thiocarbonyl analogue originates in a lower entropy of activation in the former case. The effect on the reaction rate of variation in the nature of the arene and of the entering ligand has been investigated.
An approach to hormonal receptor assay involving the detection by FT-IR spectroscopy of Cr(CO)(,3)-labelled modified estradiol bound to estrogen receptors in target tissue is reported.
The FT-IR spectra of FeTPP(CX) FeTPP = (5,10,15,20-tetraphenyl-porphinato)Fe(II); X = S, Se and FeTPP(CX)L (X = S, Se; L = pyridine, ethanol) have been obtained. Some changes in the porphyrin spectrum were observed with variation or removal of L, but not with variation of X.

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11

Keiller, B. T. "The vibrational spectra of metal cluster compounds containing organic ligands". Thesis, University of East Anglia, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.383722.

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12

何毅雯 e Ngai-man Emmie Ho. "The chemistry of ruthenium carbonyl clusters containing nitrene and nitrido ligands". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2000. http://hub.hku.hk/bib/B3124029X.

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13

Ho, Ngai-man Emmie. "The chemistry of ruthenium carbonyl clusters containing nitrene and nitrido ligands /". Hong Kong : University of Hong Kong, 2000. http://sunzi.lib.hku.hk/hkuto/record.jsp?B21982351.

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14

Li, Yat. "Syntheses, structural characterization and electrochemistry of tetraosmium carbonyl clusters and catalytic properties of tetraosmium-gold mixed-metal clusters /". Hong Kong : University of Hong Kong, 2002. http://sunzi.lib.hku.hk/hkuto/record.jsp?B25155064.

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15

Curtis, H. "Synthesis, characterisation and reactivity of transition metal carbido-carbonyl cluster and other organometallic compounds". Thesis, University of Cambridge, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.377825.

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16

Wasmund, Eric Bain Coley Ken. "A study of powder making by the decomposition of nickel carbonyl in an aerosol tube reactor". *McMaster only, 2005.

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17

Potratz, Christopher M. "The Synthesis, Structure and Characterization of Extended Cobalt Ruthenium Carbonyl Compounds". The Ohio State University, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=osu1275413923.

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18

Ting, Fai Lung. "The chemistry of osmium and ruthenium carbonyl clusters with functionalized alkyne and phosphine ligands". HKBU Institutional Repository, 2001. http://repository.hkbu.edu.hk/etd_ra/296.

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19

李軼 e Yat Li. "Syntheses, structural characterization and electrochemistry of tetraosmium carbonyl clusters and catalytic properties of tetraosmium-gold mixed-metal clusters". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2002. http://hub.hku.hk/bib/B31243356.

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20

Middleton, Mark D. "Synthesis of novel amino acids and peptides by rearrangement of ammonium ylides generated from metal carbenoids". Thesis, University of Nottingham, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.289457.

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21

Bhattacharyya, Nripendra Kumar. "Preparation and characterization of binuclear carbonylates of the iron triad and tetranuclear carbonylates of iridium : the condensation of mononuclear hydrido carbonylates to trinuclear hybrido carbonylates of the iron triad /". The Ohio State University, 1985. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487260135356797.

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22

Buitrago, Elina. "Transition metal-catalyzed reduction of carbonyl compounds : Fe, Ru and Rh complexes as powerful hydride mediators". Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-75795.

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Abstract (sommario):

A detailed mechanistic investigation of the previously reported ruthenium pseudo-dipeptide-catalyzed asymmetric transfer hydrogenation (ATH) of aromatic ketones was performed. It was found that the addition of alkali metals has a large influence on both the reaction rate and the selectivity, and that the rate of the reaction was substantially increased when THF was used as a co-solvent. A novel bimetallic mechanism for the ruthenium pseudo-dipeptide-catalyzed asymmetric reduction of prochiral ketones was proposed. There is a demand for a larger substrate scope in the ATH reaction, and heteroaromatic ketones are traditionally more challenging substrates. Normally a catalyst is developed for one benchmark substrate, and a substrate screen is carried out with the best performing catalyst. There is a high probability that for different substrates, another catalyst could outperform the one used. To circumvent this issue, a multiple screen was executed, employing a variety of ligands from different families within our group’s ligand library, and different heteroaromatic ketones to fine-tune and to find the optimum catalyst depending on the substrate. The acquired information was used in the formal total syntheses of (R)-fluoxetine and (S)-duloxetine, where the key reduction step was performed with high enantioselectivities and high yield, in each case. Furthermore, a new iron-N-heterocyclic carbene (NHC)-catalyzed hydrosilylation (HS) protocol was developed. An active catalyst was formed in situ from readily available imidazolium salts together with an iron source, and the inexpensive and benign polymethylhydrosiloxane (PMHS) was used as hydride donor. A set of sterically less demanding, potentially bidentate NHC precursors was prepared. The effect proved to be remarkable, and an unprecedented activity was observed when combining them with iron. The same system was also explored in the reduction of amides to amines with satisfactory results.

At the time of doctoral defense, the following paper was unpublished and had a status as follows: Paper 2: Manuscript.

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23

Zhang, Shulin. "Studies of Solvent Displacement from Solvated Metal Carbonyl Complexes of Chromium, Molybdenum, and Tungsten". Thesis, University of North Texas, 1990. https://digital.library.unt.edu/ark:/67531/metadc331992/.

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Abstract (sommario):

Flash photolysis techniques were applied to studies of solvent displacement by Lewis bases (L) from solvated metal carbonyl complexes of Cr, Mo, and W. On the basis of extensive studies of the reaction rate laws, activation parameters , and linear-free-energy-relationships, it was concluded that the mechanisms of solvent displacement reactions depend on the electronic and steric properties of the solvents and L, as well as the identities of the metal atoms. The strengths of solvent-metal bonding interactions, varying from ca. 7 to 16 kcal/mol, and the bonding "modes" of solvents to metals are sensitive to the structures of the solvent molecules and the identities of the metal centers. The results indicate dissociative desolvation pathways for many arene solvents in (solvent)Cr(CO)_5 (solvent = benzene, fluorobenzene, toluene, etc.) complexes, and are consistent with competitive interchange and dissociative pathways for (n-heptane)M(CO)_5. Different types of (arene)-Cr(CO)_5 interactions were suggested for chlorobenzene (CB) vs. fluorobenzene and other non-halogenated arenes, i.e. via σ-halogen-Cr bond formation in the CB solvate vs. π-arene-Cr bond formation through "isolated" double bonds in solvates of the other arenes. The data also indicate the increasing importance of interchange pathways for solvent displacement from the solvates of Mo and W vs. that of Cr.

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24

Awad, Hani H. (Hani Hanna). "Thermal and Flash Photolysis Studies of Ligand-Exchange Reactions of Substituted Metal Carbonyl Complexes of Cr and Mo". Thesis, University of North Texas, 1989. https://digital.library.unt.edu/ark:/67531/metadc332097/.

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Abstract (sommario):

Thermal and flash photolysis studies of ligand-substitution reactions of cis-(pip)(L)M(CO)_4 by L' (pip = piperidine; L, L' = CO, phosphines, phosphites; M = Cr, Mo) implicate square-pyramidal [(L)M(CO)_4], in which L occupies a coordination site in the equatorial plane, as the reactive species. In chlorobenzene (= CB) solvent, the predominant species formed after flash photolysis and a steady-state intermediate for the thermal reaction is cis—[(CB)(L)M(CO)_4], for which rates of CB-dissociation increase with increasing steric demands of coordinated L. Rates of CB-dissociation from trans-[(CB)(L)M(CO)_4] intermediates, formed after photolysis but not thermally, exhibit no observable dependence on the steric properties of the coordinated L.

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25

Siriwardane, Upali. "Systematic syntheses of iron-triad (Fe,Ru,Os) tetranuclear clusters by redox condensation reactions of [Ru(3);CO(11)) and [Os(3);CO(11)] trinuclear carbonylates; co-crystallization of ruthenium-osmium clusters /". The Ohio State University, 1985. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487264603216477.

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26

Daghetta, M. A. A. "USE OF POLIPHOSPHANES IN THE ASSEMBLY OF DISCRETE OR POLYMERIC COORDINATION COMPOUNDS". Doctoral thesis, Università degli Studi di Milano, 2010. http://hdl.handle.net/2434/155259.

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Abstract (sommario):

Although phosphanes show useful features for the coordination chemistry, their use as pure structural building blocks, to join metal centres in larger aggregates, has not been yet well explored. In this work, synthesis and characterization of discrete and polymeric coordination compounds are presented. As metal centres both monometallic and cluster compounds have been used, whereas as ligands we have used poliphosphanes both commercially available and synthesised in our laboratories. For simplicity we can classify them in: rigid diphosphanes, flexible diphosphanes and rigid poliphosphanes.

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27

Zheng, Jianxia. "Earth-abundant metal complexes for catalyzed hydroelementation". Thesis, Rennes 1, 2014. http://www.theses.fr/2014REN1S148/document.

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Ce travail de recherche est consacré au développement de catalyseurs à base de métaux de transition abondants de la première rangée du tableau périodique, tels que Mn, Fe, et Ni, pour les réactions d'hydro-élémentation. Tout d'abord, l'hydrosilylation de cétones et d'aldéhydes a été accomplie en utilisant un système catalytique simple Ni(OAc)₂ 4H2O/PCy₃ avec le PMHS, silane peu coûteux et stable en tant que source d'hydrure. L'amination réductrice d'aldéhydes avec des amines a également été réalisée avec le même système catalytique et le TMDS, comme silane. Deuxièmement, l’efficacité des complexes de manganèse demi-sandwich CpMn(CO)₂(IMes) a été prouvée pour la réduction des aldéhydes et des cétones en présence de Ph₂SiH₂ (1,5 équiv.) sous irradiation UV. La transformation difficile d'acides carboxyliques en aldéhydes a été effectuée à l'aide de Mn₂(CO)₁₀ et de Et3SiH. Troisièmement, la méthylation des amines secondaires avec le carbonate de diméthyle en tant que source C1 a été démontrée dans des conditions catalytique douces avec [CpFe(CO)₂(IMes)]I. Ensuite, l'hydroboration d'alcènes et d'alcynes fonctionnalisés a été réalisée en présence d’un complexe de fer (0), Fe(CO)₄(IMes) sous irradiation UV. Enfin, la réaction d'hydroboration a été étendue avec succès à la réduction de CO₂ en methoxyboranes avec Fe(CO)₃[P(OPh)₃]₂ en tant que catalyseur et les diverses sources de borane, tels que HBpin, HBcat ou 9-BBN
This research work deals with the use of the catalysts based on the earth-abundant transition metals of the first row of the periodic table, such as Mn, Fe, and Ni, for hydroelementation reactions. First of all, the hydrosilylation of aldehydes and ketones was accomplished using a simple Ni(OAc)₂ 4H₂O/PCy₃ catalytic system with the inexpensive and stable silane PMHS as the hydride source. The reductive amination of aldehydes with amines was also achieved with the same catalytic system and TMDS, as the silane. Second, the efficiency of manganese half-sandwich complex CpMn(CO)₂(IMes) was exemplified for the reduction of aldehydes and ketones in the presence of Ph ₂ SiH ₂ (1.5 equiv.) under UV irradiation at room temperature. Still with manganese, the challenging transformation of carboxylic acids to aldehydes was performed using commercial Mn₂ (CO)₁₀ and Et₃SiH. Third, the methylation of the secondary amines with dimethyl carbonate as an alternative and safe C1 source was demonstrated under mild conditions with [CpFe(CO)₂(IMes)]I as the catalyst. Then, the hydroboration of functionalized alkenes and alkynes was catalyzed by an iron(0) carbonyl complex Fe(CO)₄(IMes) under UV irradiation. Finally, the hydroboration reaction was successfully extended to the reduction of CO₂ to methoxyboranes with Fe(CO)₃[P(OPh)₃]₂ as the catalyst and the borane sources, such as HBpin, HBcat or 9-BBN

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28

Naeemi, Qaseem [Verfasser]. "Studies in Enantioselective Transition Metal Catalysis Using Modular Phosphine-Phosphite Ligands Copper-catalyzed 1,4-Addition of Grignard Reagents to alpha,beta-Unsaturated Carbonyl Compounds / Qaseem Naeemi". München : Verlag Dr. Hut, 2012. http://d-nb.info/1020299428/34.

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29

Abdali, Abdelkrim. "Fonctionnalisation de complexes polyeniques de fer-tricarbonyle : nouvelles voies d'acces aux dienones silylees aux trienes gem-difonctionnels et aux epoxydienes". Université Louis Pasteur (Strasbourg) (1971-2008), 1988. http://www.theses.fr/1988STR13103.

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30

SEMRA, ASSIA. "Substitutions nucleophiles en serie arenetricarbonylchrome". Paris 6, 1987. http://www.theses.fr/1987PA066622.

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31

Nuel, Didier. "Etude de la reactivite de fragments alkylidynes dans des clusters trinucleaires du fer". Toulouse 3, 1986. http://www.theses.fr/1986TOU30206.

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Abstract (sommario):

Reactivite des complexes fe::(3)(co)::(9)(cch::(3))(coc::(2)h::(5)) ou fe::(3)(co)::(10)(cch::(3))(h). Les reactions de couplage des groupes alkylidynes avec les algues sont faciles. L'action de co a mis en evidence le couplage reversible dans des conditions douces de 2 fragments alkylidynes. En general, la presence du coordinat hydruro rend les reactions plus complexes

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32

Rouida, Bouchaïb. "Syntheses diastereoselectivites de complexes chiraux du molybdene et du fer carbonyle par action de derives asymetriques du phosphore". Paris 6, 1988. http://www.theses.fr/1988PA066515.

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Abstract (sommario):

La reaction photochimique de plusieurs phosphines asymetriques avec des complexes carbonyles du fer et du molybdene cyclopentadienyls fournit des complexes chiraux. Ceux-ci se forment par couples de diastereoisomeres en proportions variables. L'effet sterique de ces phosphines sur le mecanisme de reaction est etudie. D'autre part, lorsque le complexe cyclopentadienyl carbonyle du fer comporte une liaison fer-silicium, fer-germanium ou fer-etain il se produit des interactions conduisant a des inductions diastereotopiques importantes

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33

Jund, Rodolphe. "Electrochimie de clusters mixtes tetrametalliques". Université Louis Pasteur (Strasbourg) (1971-2008), 1987. http://www.theses.fr/1987STR13175.

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34

Neff, Denis. "Complexes alleniques de cyclopentadienyle manganese dicarbonyle : acces aux allenes optiquement actifs, etude de photodecomplexations et syntheses de complexes difonctionnels". Université Louis Pasteur (Strasbourg) (1971-2008), 1988. http://www.theses.fr/1988STR13122.

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35

GOMES, DE LIMA LUIS CARLOS. "Reactions d'alcynes cyanes (monocyanoacethylene et dicyanoacethylene), vis-a-vis de complexes organometalliques du fer, du cobalt, du molybdene et du tungstene". Brest, 1986. http://www.theses.fr/1986BRES2009.

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Abstract (sommario):

Etude de la reactivite de complexes thiolates du fer et du tungstene (cp(co)::(n) m(sch::(3))) vis a vis du mono et du dicyanoacetylene. Aptitude des complexes de co(i) a intervenir dans la formation de molecules organiques. Nature des liaisons m-pb(m=mo ou w) dans les complexes cp(co)::(3)m-pbr::(3) et (cp(co)::(3)m)::(2) pbr::(2). Donnes de rmn de **(95)mo et **(207)pb

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36

Greene, Timothy Michael. "Spectroscopic and structural studies of some reactive hydride and organometallic compounds". Thesis, University of Oxford, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.282165.

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37

Caminade, Anne-Marie. "Stabilisation par complexation d'entites phosphorees de basse coordinence". Toulouse 3, 1988. http://www.theses.fr/1988TOU30073.

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Abstract (sommario):

On obtient selon le substituant organique du phosphore, des complexes de phosphines, diphosphanes halogenes et de derives phosphores a base coordinence (phosphine, phosphalcine, diphosphine, phosphacumulene

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38

Wu, Guanmin Richmond Michael G. "Synthesis characterization, and kinetics of isomerization, C-H and P-C bond activation for unsaturated diphosphine-coordinated triosmium carbonyl clusters". [Denton, Tex.] : University of North Texas, 2008. http://digital.library.unt.edu/permalink/meta-dc-6037.

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39

Gomes, de Lima Bernardes Miriam. "Réactivité de complexes organométalliques mono- et dinucléaires : synthèse de thiolato-composés du molybdène, du tungstène et du cobalt : étude de la formation de liaisons c-c dans la sphère de coordination du métal". Brest, 1986. http://www.theses.fr/1986BRES2008.

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Caracterisation des complexes ((c::(5)h::(5))(co)::(2) lwc(cf::(3)) = c(cf::(3))h) et (c::(5)h::(5))(co) lwc(o)c(cf::(3)) = c(cf::(3))h) (l=co,pr::(3),p(or)::(3)) synthese de complexes dinucleaires de mo et w. L'addition oxydante de dialkylsulfure a des derives biportes de mo(ii) et w(ii) a donne lieu a la formation de complexes thiolato triportes ((c::(5)h::(5))(co)m(mu -sr)::(3)m(co)(c::(5)h::(5)))tx**(-)

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40

Foulet-Fonseca, Gloria. "Etude par spectroscopie vibrationnelle des complexes méthylcarbyniques et méthylcarbéniques de chrome". Paris 13, 1987. http://www.theses.fr/1987PA132028.

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Etude en particulier de complexes, du type br(co)::(4)crcch::(3), br(co)::(4)crcchd::(2) et d'une série de mélanges isotopiques. Mise en évidence de la non-équivalence des liaisons c-h du groupe methyle. Etablissement d'un champ de forces pour les complexes méthylcarbyniques

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41

Lock, S. J. "Water-tolerant organometallic reactions : nucleophilic additions to carbonyl compounds using allyl metals in aqueous solution". Thesis, Swansea University, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.637942.

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Against a background of the reactivity of traditional organometallics, this work describes nucleophilic addition reactions that take place via the intervention of metals in the presence of water. The experimental work focuses on allylation of aldehydes in water-containing solvents using nickel, bismuth and aluminium. Chapter 1 outlines the current influence of environmental issues on the practice of chemistry and the value of water as a solvent. Carbon-carbon bond formation is discussed in the context of mechanism and common methods are reviewed, particularly with respect to reaction of the carbonyl functional group. A sample of the well-established organometallic reagents are examined in terms of their characteristics and general reactivity, which then serve as a backdrop to a description of the types of metal-mediated reactions that occur in aqueous solutions. Chapter 2 describes allylation reactions using water-tolerant allylic metals species obtained via transmetallation between metal salts and allylic Grignard reagent. The properties and reactions of a nickel-containing allylating agent are examined in greater detail. Chapter 3 describes bismuth-mediated reactions in which zero-valent bismuth is generated in situ from a bismuth salt and a reducing metal in entirely aqueous solution. Chapter 4 examines the potential of using aluminium to promote allylation reactions in aqueous solutions. Chapter 5 focuses on allylations using bismuth powder in entirely aqueous solutions and the influences of a variety of additives. The scope and mechanism of reactions performed in potassium fluoride solution are explored in more detail.

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42

Etienne, Michel. "Réactivité de complexes dinucléaires hydrure et alcénylidène ponte du fer vis-a-vis d'hydrocarbures cyanes insatures (mono et dicyanoacétylène, tétracyanoethylène)". Brest, 1988. http://www.theses.fr/1988BRES2009.

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Preparation de complexes avec des coordinats cyano-4 butadienyldene portants. On obtient egalement des complexes dinucleaires avec le tricyano-3,4,4 butadienylidene-1,3. Mecanisme ses reactions de migration de l'hydrogene allylique

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43

Laurent, Pascale. "Complexes acyl, alcoxycarbonyl et alkyl tetracarbonylfer : intermédiaires dans la carbonylation catalytique d'halogénures d'alkyle". Brest, 1989. http://www.theses.fr/1989BRES2002.

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44

Holmes, Brett. "Mobilization of Metals and Phosphorous from Intact Forest Soil Cores by Dissolved Inorganic Carbon: A Laboratory Column Study". Fogler Library, University of Maine, 2007. http://www.library.umaine.edu/theses/pdf/HolmesB2007.pdf.

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45

Achi, Sabah Samira. "Nouvelle voie d'acces aux acides alpha -amines, par catalyse homogene a l'aide de complexes de metaux de transition, synthese de nouveaux complexes phosphores chiraux du tungstene pentacarbonyle". Paris 6, 1987. http://www.theses.fr/1987PA066227.

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46

Odongo, Onduru Stephen. "Rhenium(I) tricarbonyl complexes synthesis, photophysics, swithing and recognition properties /". Diss., Online access via UMI:, 2005.

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47

Bates, Sarah Anne. "Fourier transform infrared isotopic studies on novel metal-carbon clusters trapped in Ar matrix environments". [Fort Worth, Tex.] : Texas Christian University, 2008. http://etd.tcu.edu/etdfiles/available/etd-04222008-113234/unrestricted/bates.pdf.

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48

Wang, Yi. "Metal-organic and organic photosensitizers for photocatalytic hydrogen generation and carbon dioxide reduction". HKBU Institutional Repository, 2017. https://repository.hkbu.edu.hk/etd_oa/414.

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This thesis is focused on developing metal-organic and organic molecules for photocatalytic water splitting and carbon dioxide reduction. In chapter 1, an overview of hydrogen production, dye-sensitized solar cells and carbon dioxide reduction are provided. The development history and reaction mechanisms of catalytic systems are introduced along with the typical examples in each field. The applications of both metal-organic and organic compounds are covered. In chapter 2, nine molecular organic photosensitizers were designed and synthesized. The nine molecules were employed as the photosensitizing reagent in the fabrication of dye-sensitized solar cells and applied in photocatalytic water reduction via coupling with TiO2 semiconductors and Pt co-catalyst. The highest turnover number (TON) of 10200 was achieved by organic photosensitizer 1g for hydrogen generation. The effect of alkyl chains and triarylamine donor moiety to the photocatalytic performance was investigated. A shorter alkyl chain was found to favor the reaction due to a lower hydrophobicity which in turn may block the interaction between the photocatalyst and water molecules. Besides, the triarylamine donor units facilitated high hydrogen generation rates by reducing the contact between catalytic active sites and the oxidized form of sacrificial reagents. In chapter 3, five earth-abundant metal complexes were synthesized to serve as the catalyst and CdS nanorods (NRs) were prepared to be the photosensitizer for the photocatalytic water reduction. A cobalt dithiolene complex (2a) achieved a TON of 30635 in 20 h under the blue light irradiation at a concentration of 10 µM. A new complex 2c also gave a high TON of 12375 under the same conditions and its TON was further improved to 115213 in 87 h by reducing the concentration of catalyst by ten times. The size effect of CdS NRs was investigated and larger nanoparticles exhibited higher hydrogen production rates. In chapter 4, ten iridium(III) complexes were synthesized and used as dual-functional molecules in photocatalytic carbon dioxide reduction by acting as both the photosensitizing reagent as well as the catalyst. The best performance was achieved by 3j, giving a TON of 230 under the irradiation of blue LED. A push-pull effect brought by trifluoromethyl and methoxy group sucessfully enhanced the carbon dioxide reduction efficiency. The hydrophobicity of n-butyl chain also provided effective protection to the active sites of reaction intermediate. Additional steric hindrance was found to extend the lifespan of photocatalytic systems but led to a drop in the overall conversion efficiency. Chapter 5 summarizes the specific synthetic procedures and characterization parameters of the molecules in chapters 2-4.

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Ying, Fang. "Au/CeO₂ based catalysts for catalytic oxidation of volatile organic compounds and carbon monoxide". HKBU Institutional Repository, 2010. http://repository.hkbu.edu.hk/etd_ra/1185.

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Yang, Ning. "Synchrotron Diffraction Studies of Spontaneous Magnetostriction in Rare Earth Transition Metal Compounds". Washington, D.C. : Oak Ridge, Tenn. : United States. Dept. of Energy. Office of Science ; distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy, 2004. http://www.osti.gov/servlets/purl/835381-gxv1Km/webviewable/.

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Tesi sul tema "Metal carbonyl compounds"

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