Thèses : « Group IV metals »

1

Janeway, Felix David. « Aluminium and group IV metals for polymerisation of lactide ». Thesis, University of Leeds, 2015. http://etheses.whiterose.ac.uk/12492/.

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The overall aim of this project is to broaden the understanding of the polymerisation of lactide to make poly(lactic acid). The major uses of poly(lactic acid) are in the household, replacing petroplastics to make disposable items such as plastic bags. During this project, new catalysts for the polymerisation of lactide will be synthesised, with both electron poor and electron precise target molecules being identified in order to discover useful replacements for current catalysts. Study of the mechanism of the polymerisation of lactide will be achieved by variation of the steric and electronic properties of the catalysts, as insights into the mechanism of the polymerisation may also give ideas as to how to better design viable industrial alternatives to those compounds already established. Target molecules will be tested for their ability to polymerise lactide to discover motifs which are efficient at synthesising poly(lactic acid), as well as exploring those motifs which are traditionally avoided for polymerisation of lactide. The nature of the polymers obtained will be investigated, and qualifications of what makes a useful polymer for industrial use defined. The project will investigate the possible products formed after polymerisation, and attempts will be made to exploit the structure of a catalyst to impart functionality into the polymer chain itself. Some of the target molecules of this project are also expected to have anti-cancer properties, so their anti-cancer activity will be assessed in vitro, and polymers made using anti-cancer active catalysts will be tested for anti-cancer activity.

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Jaggar, Andrew James. « The synthesis and reactions of cationic alkyl complexes of group(IV) transition metals ». Thesis, University of East Anglia, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.332355.

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Gribkov, Denis. « Novel catalysts for stereoselective hydroamination of olefins based on rare earth and group IV metals ». [S.l.] : [s.n.], 2005. http://deposit.ddb.de/cgi-bin/dokserv?idn=976595567.

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4

Lapenta, Rosita. « New metal catalysts for the synthesis of polyolefins and bioderived polymers ». Doctoral thesis, Universita degli studi di Salerno, 2018. http://hdl.handle.net/10556/2980.

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2016 - 2017
The aim of PhD project is the synthesis of new metal catalysts active in the polymerization of polar monomer and α-olefins. In the last decade, transition metal complexes bearing tetradentate bis(phenolato) ligands are widely studied for their high polymerization control and activity.1 The bis(phenolato) ligand is composed of two phenoxide groups linked by a bridge comprising two donor heteroatoms; when the donors are two sulfur atoms, the ligand is called of OSSO-type... [edited by Author]
XXX ciclo

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Patel, Bhavesh. « Hard/soft interactions : Group IV metal halide complexes with soft donor ligands of Groups 15 and 16 ». Thesis, University of Southampton, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.395952.

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Lundberg, Helena. « Group (IV) Metal-Catalyzed Direct Amidation : Synthesis and Mechanistic Considerations ». Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-116955.

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The amide unit constitutes the backbone of proteins, and it is present in a large number of pharmaceutically active molecules, polymeric materials such as nylon and Kevlar, as well as in food additives like aspartame. Amides are produced in enormous amounts every year, thus, environmentally friendly and selective methods for their formation are of great importance. This thesis deals with the direct formation of amides from non-activated carboxylic acids and amines with the aid of group (IV) metal complexes. Water is the only by-product of this environmentally benign process. This fact stands in contrast to the most common methods for amide formation to date, which involve the use of waste-intensive, expensive and often toxic coupling reagents. The catalytic protocols presented herein use titanium, zirconium and hafnium complexes under mild reaction conditions to produce amides in good to excellent yields. Furthermore, carbamates are demonstrated to be suitable sources of gaseous amines for the formation of primary and tertiary amides under catalytic conditions. In addition, preliminary results from on-going mechanistic investigations of the zirconium- and hafnium-catalyzed processes are presented.
Amidbindningen är en kemisk enhet som utgör ryggraden i proteiner, och som även återfinns i en stor mängd läkemedelsmolekyler, polymera material som nylon och Kevlar, samt i tillsatser i livsmedelsindustrin, exempelvis aspartam. Amider produceras i enorma mängder varje år, och det är av stor vikt att utveckla miljövänliga och selektiva metoder för deras framställning. Denna avhandling behandlar direkt amidering av icke-aktiverade karboxylsyror och aminer med hjälp av katalytiska mängder metallkomplex, baserade på titan, zirkonium och hafnium. Den enda biprodukten från denna amideringsreaktion är vatten. Jämfört med de metoder som generellt används idag för amidsyntes, så är de presenterade metoderna avsevärt mer miljövänliga med avseende på toxicitet hos reagensen såväl som på mängden avfall som genereras. Dessutom redovisas här en katalytisk metod för syntes av primära och tertiära amider genom att använda olika karbamat som källa till gasformiga aminer, vilka annars kan vara praktiskt svåra att arbeta med. Preliminära resultat från en pågående mekanistisk studie av de zirkonium- och hafnium-katalyserade processerna är också inkluderade.

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

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Theurkauff, Gabriel. « Investigations on the stereoselective polymerization of α-olefins by single-site group IV metal catalysts ». Thesis, Rennes 1, 2014. http://www.theses.fr/2014REN1S158/document.

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Les travaux présentés dans ce manuscrit ont trait à la catalyse de polymérisation des α-oléfines sont présentés en 4 parties distinctes. La première est consacrée à l'étude d'un système catalytique pour la production de polypropylène élastomère. L'analyse poussée des polymères produits et la caractérisation complète des catalyseurs utilisés a permis de montrer la présence de deux homopolymères sous forme de blende. La seconde partie porte sur la copolymérisation de monomères bifonctionnels vinyl-vinylidène avec le propylène. La caractérisation des polymères a permis de révéler la réactivité particulière des liaisons vinylidène et d'étudier l'influence du catalyseur utilisé sur le mécanisme de la polymérisation. La troisième partie s'intéresse à la caractérisation des espèces active en polymérisation et à l'étude des mécanismes d'activation et de désactivation des catalyseurs métallocènes. La synthèse et la caractérisation d'espèces cationiques, l'étude de leur comportement dynamique en solution, ainsi que l'évaluation de leur productivité en polymérisation ont permis d'établir un lien entre les propriétés électrophiles de ces espèces et de leur activité en polymérisation. La dernière partie porte sur l'homopolymérisation d'α-oléfines encombrées. La recherche d'un catalyseur suffisamment productif nous a amené à tester plusieurs catalyseurs présentant des structures différentes. L'absence de catalyseur productif soulève l'hypothèse d'interactions désactivantes entre le catalyseur et le monomère
The work presented in the manuscript focus on α-olefin polymerization catalysis, and is divided into four distinct parts. The first part is dedicated to the study of catalytic systems for the production of elastomeric polypropylene. The analysis of the produced polymers and the characterization of the catalysts showed the presence of two homopolymers as a blend in the elastomeric polypropylene. The second part focuses on the copolymerization of bifunctionnal vinyl-vinylidene monomers with propylene. The characterization of the polymers revealed the reactivity of the vinylidène bonds and showed different polymerization mechanisms for the different catalysts. The third part reports a study on the activation and deactivation pathways of the active species in polymerization. The characterization of model cationic species and the study of their behavior in solution and in polymerization showed the relationship between the electrophilicity of the species and its productivity in propylene polymerization. The last part is dedicated to the polymerization of hindered α-olefins. The quest for a productive catalyst led to test various single site catalysts with different structures. Deactivating interactions between the monomers and the catalyst are supposed to explain the low productivity of the tested catalysts

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Wintersgill, S. « Reactions of group IV metal compounds with isocyanates, and their catalytic applications ». Thesis, University of Newcastle Upon Tyne, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.311171.

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9

Thompson, Joseph. « Development of single-source CVD precursors for group IV, V and VI metal disulfides ». Thesis, University of Bath, 2017. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.715262.

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Transition metal dichalcogenides (TMDs) exhibit a wide range of interesting properties and potential applications. The major barrier to the use of these materials in devices is the formation of high quality thin films. Chemical vapour deposition (CVD) is a scalable technique which can provide high quality thin films over large areas. The principal objective of this work is to synthesise and characterise a range of single-source precursors for the deposition of metal disulfides. Chapter 1 provides an introduction to the applications, properties and synthesis of TMDs. An overview of CVD highlights the major variants used while the major classes of metal chalcogenide single-source precursors are reviewed. Chapter 2 describes the synthesis, characterisation and structures of group IV metal thioureide complexes formed by the insertion of isothiocyanates into group IV metal amides. Heteroleptic and homoleptic group IV metal dithiocarbamates are also investigated with selected complexes used as precursors in aerosol-assisted CVD (AACVD) and low pressure CVD (LPCVD) experiments. Chapter 3 describes the synthesis, characterisation and structures of tantalum thioureide complexes formed by the insertion of isothiocyanates into PDMAT or [(tBuN)Ta(NMe2)3]. Thermal decomposition studies of these complexes are discussed. tert-butylimide based tantalum dithiocarbamates are also investigated as both AACVD and LPCVD precursors for the deposition of TaS2. Chapter 4 describes the synthesis, characterisation and structures of group VI metal thioureide complexes formed by the reactions of bis(tert-butylimido)bis(amido) group VI metal complexes and either isothiocyanates or disubstituted thioureas. The suitability of these complexes as AACVD precursors is explored. Homoleptic group VI metal dithiocarbamates and xanthates are also investigated as AACVD precursors. Deposition of WS2 onto graphene substrates is studied using the precursor [W(S2CNEt2)4]. Chapter 5 contains experimental procedures and characterisation data for the complexes and thin films described. Appendix lists the crystal structure refinement tables and EDX analysis spectra.

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Loukova, G. V., V. V. Vasiliev, V. L. Ivanov, M. Ya Melnikov, V. A. Smirnov et E. E. Melnichuk. « Two−photon Processes in Organometallic Molecules and Clusters : T−T Absorption of Group IV Metal Complexes ». Thesis, Sumy State University, 2013. http://essuir.sumdu.edu.ua/handle/123456789/35395.

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Triplet – triplet absorption of d0 metal complexes was for the first time revealed and studied by means of pulse photolysis and electron-exchange (Dexter) resonant energy transfer energy transfer. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35395

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11

Zeng, Li. « Disordered electronic and magnetic systems - transition metal (Mn) and rare earth (Gd) doped amorphous group IV semiconductors (C, Si, Ge) ». Connect to a 24 p. preview or request complete full text in PDF format. Access restricted to UC campuses, 2007. http://wwwlib.umi.com/cr/ucsd/fullcit?p3284117.

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Thesis (Ph. D.)--University of California, San Diego, 2007.
Title from first page of PDF file (viewed January 9, 2008). Available via ProQuest Digital Dissertations. Vita. Includes bibliographical references (p. 123-132).

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David, Jérémy. « Étude des mécanismes de réduction carbothermique d'oxydes métalliques du groupe IV par MET : Apport de précurseurs de type polymères de coordination ». Limoges, 2013. https://aurore.unilim.fr/theses/nxfile/default/f239d478-5a37-46db-8ffc-dda194277ff8/blobholder:0/2013LIMO4013.pdf.

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Cette thèse est dédiée à l'étude des mécanismes réactionnels mis en jeu lors de la formation d'oxycarbures élaborés par différentes voies de synthèse. Elle revisite tout d'abord la littérature qui était jusque là plutôt consacrée à des approches thermochimiques et cinétiques. Ce travail original concerne une étude structurale et chimique menée principalement par microscopie électronique à transmission (MET) et par diffraction des rayons X (DRX) sur des échantillons obtenus à des degrés d'avancement variables de réactions. La première partie de cette étude est consacrée aux voies classiques de transformation carbothermique mettant en jeu des dioxydes (TiO2, ZrO2, HfO2) réduit en oxycarbures au contact de noir de fumée. Nous montrons que les mécanismes réactionnels mis en jeux lors de la déstabilisation des phases parents sont intrinsèquement liés à la structure des dioxydes et que la taille initiale des cristallites d oxydes n’a pas d’influence sur celle des oxycarbures formés. Le site de nucléation de l'oxycarbure ainsi que les mécanismes de croissance ont également été mises en évidence et discutés. Une seconde partie du manuscrit est consacrée à une étude originale visant à synthétiser des carbures à partir de polymères de coordination (MOF pour Metal-Organic Frameworks). La transformation progressive des précurseurs en oxycarbure est étudiée en détail et nos résultats montrent que les mécanismes mis en jeu lors de cette transformation s'apparentent beaucoup à ceux mis en évidence dans le cadre des réactions carbothermiques classiques
This thesis is dedicated to the study of the reactional mechanisms involved in the formation of oxycarbides by different synthesis routes. It reconsiders the literature that used to deal with thermochemical and kinetical approaches. This original work deals with a structural and chemical study mainly led by transmission electron microscopy (TEM) and X-ray diffraction (XRD) on samples obtained at different advancement rates. The first part of this study is about the classical carbothermal reduction transformations of dioxides (TiO2, ZrO2, HfO2) reducted by carbon black into oxycarbide. We highlight that the reactional mechanisms involved into the parent phases destabilization are intrinsically linked to the dioxides structure and that the initial size of oxide particles has no influence on the ones of the oxycarbides. The nucleation site of the oxycarbide and the growth mechanisms have also been highlighted and discussed. A second part of the manuscript is dedicated to an original study aiming to synthesize carbide from Metal-Organic Frameworks (MOF). The progressive transformation of the precursors into oxycarbides is very likely to the ones highlighted in the field of classical carbothermal reactions

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Haas, Isabelle [Verfasser], et Rhett [Akademischer Betreuer] Kempe. « Novel N-Ligand Stabilized Transition Metal Complexes of the Group IV Triad as Efficient Catalysts for Polymerization and Oligomerization / Isabelle Haas. Betreuer : Rhett Kempe ». Bayreuth : Universität Bayreuth, 2013. http://d-nb.info/106000948X/34.

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Gribkov, Denis [Verfasser]. « Novel catalysts for stereoselective hydroamination of olefins based on rare earth and group IV metals / vorgelegt von Denis Gribkov ». 2005. http://d-nb.info/976595567/34.

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Tzer, An Hung, et 洪澤安. « Group IV Element Metal-Oxide-Semiconductor Light Emitting Devices ». Thesis, 2008. http://ndltd.ncl.edu.tw/handle/62421984380314050293.

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碩士
國立臺灣大學
電子工程學研究所
96
In this thesis, various metal-oxide-semiconductor light-emitting-devices (MOS LED) were fabricated and investigated of their luminescence characteristics. The MOS LED structures include the Ge MOS LED with silicon dioxide (SiO2), Ge MOS LED with aluminum oxide (Al2O3) and the 6H-SiC MOS LED. Infrared emission is observed from the Ge MOS LED. A spectral line fit is performed on the luminescence spectrum with the electron-hole-plasma (EHP) recombination model with 5 phonon assisted replica, including TO, LA, TA emission, and TA, LA absorption. Intensity of the TA phonon absorption is seen to increase at elevated temperatures. Reduced thermal quenching in electroluminescence compared to photoluminescence measurements is due to the large difference in concentration between the majority and minority carriers in EL, which limits the cause of the decrease of radiative recombination probability to only the lowering of the minority concentration. The Ge MOS LED with Al2O3 insulator shows improvements in performance that include smaller operating voltage, smaller leakage current, stronger light emission, reduced nonradiative radiation and an increase in light emission intensity at elevated operation temperatures. Blue luminescence at reverse bias is observed in the 6H-SiC MOS LED.

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Lan, Huang-Siang, et 藍偟翔. « Electric Conduction of Group IV Alloy and Group III-V as Metal Gate Device ». Thesis, 2008. http://ndltd.ncl.edu.tw/handle/37951531957492049608.

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碩士
國立臺灣大學
電子工程學研究所
96
Abstract In this thesis, three topics are included. One is the direct band gap Ge1-xSnx alloys simulated by valence band anti-crossing method and nonlocal empirical pseudopotential method and the other is the Si-like (x<0.85) strained Si1-xGex N-MOSFETs mobility calculations which include alloy scattering, phonon scattering and roughness scattering. Lastly, Poly-III-V compound semiconductor was proposed to be used as gate electrode first time. Part I : For a long time, group IV semiconductors applied on photoelectric devices have been limited in efficiency by nature indirect band gap. Tensile strained Ge can also be a direct band gap material in theoretical simulations, but not easy to fabricate in practice. However, Ge1-xSnx alloys can form the narrow direct band gap and have been fabricated in the reported experiments successfully. Ge1-xSnx alloys can be applied on infrared optoelectronic applications and may be fabricated new high speed transistors further. In this thesis, chapter 2, energy band structures of Ge1-xSnx alloys are simulated to find the possible direct band gap in group IV semiconductors. Part II : Strained silicon is the main stream to produce higher mobility in transistors. However, the reasons of increase mobility in N-MOSFETs are not only split the lower delta 2 subband and higher delta 4 subband but also change some important elements under strain. In this topic, chapter 3, we simulate the mobility of Si on Si1-xGex substrates and Si1-xGex on Si1-xGex substrates N-MOSFETs and include difference kinds of scattering effects. Part III : As High-k dielectrics were used to replace conventional SiO2 as insulators of MOSFETs, poly-silicon gate must also been replaced by different kinds of metals. In this topic, chapter 4, ploy-III-V semiconductor was fabricated as gate electrode of metal-oxide semiconductors (MOS) first time. Utilizing band gap of III-V semiconductor can adjust the work function and the results of experiments were discussed.

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Lan, Huang-Siang. « Electric Conduction of Group IV Alloy and Group III-V as Metal Gate Device ». 2008. http://www.cetd.com.tw/ec/thesisdetail.aspx?etdun=U0001-1307200813282900.

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Kumar, Akshai A. S. « Reductive And Metathetic Coupling Reactions Mediated By Group (IV) Metal Alkoxides ». Thesis, 2009. http://hdl.handle.net/2005/919.

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Several organic transformations are mediated by group(IV) metal alkoxides. The reactivity is based on the basic nature of alkoxide group, Lewis acidic nature of the group(IV) metals, insertion of unsaturated molecules into the M-OR bond and the reduction of M(OR)4 to low valent species. The thesis deals with insertion reactions and the reductive and metathetic coupling reactions mediated by group(IV) metal alkoxides. Titanium(IV) alkoxides and zirconium(IV) alkoxides promote insertion and metathesis of aryl isocyanates. It was observed that aryl isocyanates underwent double insertion in addition to mono insertion. At room temperature, head to tail double insertion is observed whereas at elevated temperatures, head to head double insertion occurred leading to metathesis. The reaction has also been extended to metathesis between heterocumulenes and heteroalkenes. Titanium and zirconium carry out these reactions with different efficiencies. The reasons for these differences have been sought through computational methods. New organic transformations promoted by group(IV) metal alkoxides that are reduced with Grignard reagents and silanes have been explored. Grignard reagents do show reactivity towards imines in the presence of group(IV) metal alkoxides. The reactions have been studied with stoichiometric and catalytic amounts of titanium(IV) isopropoxide and are shown to follow different pathways. Isotope labeling studies indicate that alkylated products formed in stoichiometric reactions arise due to metal-olefin intermediates. However in catalytic reactions, a metal-alkyl complex is responsible for alkylation. Titanium(IV) alkoxides when used in combination with silanes such as phenylsilane bring about the reductive coupling of imines. One of the interesting features is that this pinacol type coupling is diastereospecific.

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19

LUCONI, LAPO. « “Group-IV Organometallics for the Catalytic Polymerization and Hydroamination of Unactivated Olefins” ». Doctoral thesis, 2014. http://hdl.handle.net/2158/835116.

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The thesis work aims at providing new insights and perspectives in the field of oligomerization/polymerization catalysis mediated by early metal complexes stabilized by ligands containing nitrogen donor groups. To make an additional step forward, widening the catalyst application range, most of the developed catalytic systems have been scrutinized with respect to their ability to promote different catalytic cycles related to the production of various materials and commodities. Accordingly, neutral and/or cationic catalysts capable to engage in highly efficient -olefin polymerization have also been successfully employed in the intramolecular hydroamination reaction of model primary and/or secondary aminoalkenes for the obtainment of pyrrolidine and/or piperidine heterocycles.

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Brusich, Mark John. « Theoretical Insights into the Bonding in Thorium Organometallic Complexes : A Comparison with Group IV Transition Metal Chemistry ». Thesis, 1988. https://thesis.library.caltech.edu/5307/4/Brusich_MJ_1988.pdf.

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In this thesis a detailed ab initio theoretical study of organothorium chemistry is presented. The first part is devoted to examining both the bonding in and the reaction chemistry of various substituted thorium complexes. Using the chlorine ligand as a model for the usual cyclopentadienyl groups found in these systems, we examine the bonding of hydrogen and methyl ligands to thorium. Frequent comparisons with the experimental results on similar species are made. In addition, by contrasting the bonding in the thorium complexes with the bonding in the analogous Group IVB systems, a qualitative and quantitative picture of bonding, as the atomic number of the metal becomes larger, can be obtained. The reaction chemistry is studied via two different sets of processes. In the first, the deuterium (D₂) exchange reaction with a thorium-hydrogen bond is examined. Several studies have been done previously, both experimentally and theoretically, on the Group IVB exchange reactions. Hence, there is enough information to see trends and to make predictions about relative reaction rates. Also, from our investigation the effect that different types of ligands have on the activation barrier to reaction can be ascertained.

In the second part of the thesis, the factors that go into stabilizing bond formation are discussed concerning both main group elements and transition metals, including actinides. In particular, the process of bond formation between hydrogen atom and the alkali metals is compared with the same process in the Group IVB-hydrogen and thorium-hydrogen saturated complexes. The main difference between the alkali metal and the transition metal bonds with hydrogen is the bond strength trends with increasing atomic number. For the alkali metals the bond energies decrease down the column, yet for the transition metals and thorium it is the reverse. The conclusion is that the shape of the mostly d in character transition metal bonding orbitals is such that better overlap can be achieved with hydrogen as the orbitals become more diffuse. In the alkali metals the bonds can be described as s—s bonds whose overlap decreases with increasing diffuseness.

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Tsai, Jie-Ying, et 蔡杰穎. « Aluminum, Zinc and Group IV Metal Complexes Containing Ketiminate Ligands. Synthesis, Characterization, and Ring-Opening Polymerization of ε-Caprolactone ». Thesis, 2016. http://ndltd.ncl.edu.tw/handle/3a6zan.

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碩士
國立彰化師範大學
化學系
104
A series of main and transition metal complexes containing ketiminate ligand, [OCMeCHCMeNHC6H4-2-tBu] (L1), [OCMeCHCMeNHCH2C6H4-4-Me] (L2), [OCPhCHCMeNHCH2(C4H7O)] (L3), [OCPhCHCMeNHCH2Ph] (L4), [OCMeCHCMeNHCH2(C4H7O)] (L5), [OCMeCHCMeNHCH2Ph] (L6) and [OCMeCHCMeNHMes] (L7) were synthesized and characterized. Treatment of 1 equiv of AlMe3 with L1-L4 generates aluminum complexes [AlMe2(OCMeCHCMeNC6H4-2-tBu)]（1）, [AlMe2(OCMeCHCMeNCH2C6H4-4-Me)]（2）, {AlMe2[OCPhCHCMeNCH2(C4H7O)]}（3）, [AlMe2(OCPhCHCMeNCH2Ph] （4）. Treatment of 2 equiv of L1-L7 with ZnMe2 generates Zinc complexes [Zn(OCMeCHCMeNC6H4-2-tBu) 2] （5）, [Zn(OCMeCHCMeNCH2C6H4-4-Me) 2]（6）, {Zn[OCPhCHCMeNCH2(C4H7O)]2} （7）, [Zn(OCPhCHCMeNCH2Ph)2] （8）, {Zn[OCMeCHCMeNCH2(C4H7O)]2}（9）, [Zn(OCMeCHCMeNCH2Ph)2] （10）, [Zn(OCMeCHCMeNMes)2] （11）. Treatment of 2 equiv of L6 or L7 with MR4 generates group IV complexes ML2R2 (12, M=Ti, R1=CH2Ph, R=NMe2; 13, M=Zr, R1=CH2Ph, R=NMe2; 14, M=Zr, R1=CH2Ph, R=NEt2; 15, M=Hf, R1=CH2Ph, R=NEt2; 16, M=Ti, R1=Mes, R=OiPr; 17, M=Ti, R1=Mes, R=NMe2; 18, M=Zr, R1=Mes, R=NMe2; 19, M=Zr, R1=Mes, R=NEt2; 20, M=Hf, R1=Mes, R=NEt2). All the aforementioned complexes have been characterized by 1H and 13C NMR spectroscopy and have been determined by single X-ray diffractometry in solid state (except 2, 3, 4, 7, 8, 9, 11, 12, 13, 14, 15, 19 and 20). Complexes 16, 17, 18, 19 and 20 were tested as initiators for the ring-opening polymerization of ε-caprolactone.

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Chen, Yun-Fan, et 陳韻帆. « Synthesis, Characterization and Ring Opening Polymerization of Main Group and Group IV Metal Complexes Containing Bi- or Tri-dentate Keto-amine, Furanyl-amine or Pyridyl-amine Ligands ». Thesis, 2019. http://ndltd.ncl.edu.tw/handle/g9yw9m.

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碩士
國立彰化師範大學
化學系
107
應文摘要 A series of group 4 metal and main group complexes containing bi- or tri-dentate keto-amine, furanyl-amine or pyridyl-amine ligands are synthesized and characterized. Reacting furfural with 2-(aminomethyl)pyridine and (+/-)-tetrahydrofurfurylamine in the presents of NaBH4 result new tridentate amine ligands NC5H4CH2NHCH2C4H3O (L1H) and OC4H3CH2NHCH2C4H7O (L4H), respectively. Similarly, reacting Pyridine-2-carboxaldedehyde with 2-(aminomethyl)pyridine and (+/-)-tetrahydrofurfurylamine in the presents of NaBH4 result NC5H4CH2NHCH2C5H4N (L2H) and NC5H4CH2NHCH2C4H7O (L3H), respectively. In addition, adding 2,4-pentandione with one equivalent of 2-(1-cyclohexenyl)ethylamine in methanol gives a new keto-amine ligand MeC(OH)CHCMe(CH2CH2C6H9) (L6H). Similarly, adding 2,4-pentandione with one equivalent of 2-(aminomethyl)pyridine in methanol gives a new keto-amine ligand MeC(OH)CHCMe(NCH2NC5H4) (L5H). Ligands L1H-L6H have been characterized by 1H and 13C NMR spectroscopy. Reacting ligands L1H-L6H with main group and group 4 metal amide (M(NR2)4, M = Ti, Zr, Hf; R = Me, Et) yield corresponding ligand-metal amide complexes. Characterization of these metal complexes have been performed and related catalytic reactions will be performed.

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