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Beta Diketiminate Ligands As Supports For Alkaline Earth And Aluminum Complexes Synthesis Characterization And Reactivity Studies
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Book Synopsis Beta -Diketiminate Ligands as Supports for Alkaline Earth and Aluminum Complexes: Synthesis, Characterization, and Reactivity Studies by : Sarish Sankaranarayana Pillai
Download or read book Beta -Diketiminate Ligands as Supports for Alkaline Earth and Aluminum Complexes: Synthesis, Characterization, and Reactivity Studies written by Sarish Sankaranarayana Pillai and published by . This book was released on 2009 with total page 92 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Β−diketiminate [Beta-diketiminate] Ligands as Supports for Alkaline Earth and Aluminum Complexes by : Sarish Sankaranarayana Pillai
Download or read book Β−diketiminate [Beta-diketiminate] Ligands as Supports for Alkaline Earth and Aluminum Complexes written by Sarish Sankaranarayana Pillai and published by . This book was released on 2009 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis and Characterization of Group 13 & 15 Complexes Supported by N, N'-bidentate Ligands by : Zheng Lu
Download or read book Synthesis and Characterization of Group 13 & 15 Complexes Supported by N, N'-bidentate Ligands written by Zheng Lu and published by . This book was released on 2007 with total page 442 pages. Available in PDF, EPUB and Kindle. Book excerpt: The first example of an N, N'-chelated [beta]-diketiminato phosphenium salt has been isolated by careful tuning of both the ligand architecture and the electronic characteristics of the phosphorus containing moiety. Using a two-electron reduction approach, the first example of a phosphinidene valence isomer has been isolated and structurally characterized. The mechanism of formation of this valence isomer was elucidated via Density Functional Theory (DFT) calculations. These calculations revealed that the formation of this valence isomer involves the intermediacy of a triplet diradical. In turn, the triplet diradical decays by two further steps to generate the observed product. A cationic phosphinous acid has been prepared via the hydrolysis of a cationic phosphenium complex in basic solution. DFT calculations reveals that the introduction of a positive charge stabilizes the phosphinous acid form. Two N, C-bonded phosphenium cation salts have also been obtained, the crystal structures of which reveal that the formation of these compounds involves C-H activation of a methyl group on the [beta]-diketiminate ligand. Three synthetic methods, namely halide abstraction, aluminum/boron halide exchange process and salt metathesis, have been explored for the preparation of boron cations supported by [beta]-diketiminate ligands. The first structurally characterized boron cation supported by a [beta]-diketiminate ligand has been isolated as its [Al2Cl--]− salt. A Ga-Fe organometallic complex supported by a [beta]-diketiminate ligand has also been synthesized via salt metathesis reaction and fully characterized. Finally, several bisamidinate supported boron complexes have been synthesized and structurally characterized. Such complexes may have applications as bifunctional catalysts or as building blocks for novel polymers.
Book Synopsis Novel [beta]-diketiminates and [beta]-diketiminate Derivatives for the Synthesis of Main Group Complexes by : Brant James Maitland
Download or read book Novel [beta]-diketiminates and [beta]-diketiminate Derivatives for the Synthesis of Main Group Complexes written by Brant James Maitland and published by . This book was released on 2015 with total page 480 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis is primarily concerned with the synthesis of low oxidation state alkaline earth metal complexes featuring novel [beta]-diketiminate ligands and their derivatives. The syntheses of a variety of different [beta]-diketiminates possessing extreme steric bulk, as well as those that have been electronically modified are detailed. These ligands have been used to produce a variety of different alkali metal, alkaline earth metal and lanthanide complexes.Chapter 1 provides a general introduction to low oxidation state alkaline earth metal chemistry. Particular attention is given to metal complexes featuring [beta]-diketiminates, given their central role in the research making up this thesis.Chapter 2 deals with the synthesis of a range of novel, sterically hindered [beta]-diketimines. These pro-ligands were targeted in the belief that their extreme bulk would allow the synthesis of currently unknown structural motifs.Chapter 3 is primary concerned with the exploitation of the developed sterically hindered [beta]-diketimines in the synthesis of a variety of alkali metal, alkaline earth metal and lanthanide complexes. A range of three coordinate magnesium complexes were produced using the developed ligands, most notably, the first crystallographically characterised [beta]-diketiminato magnesium hydride. In our quest for a calcium(I) dimer, a complex type which is currently unknown, a variety of [beta]-diketiminato calcium iodides were produced. The attempted reduction of these heteroleptic metal iodide complexes resulted not in the targeted low oxidation state complexes, but in two different calcium(II) dimers.In Chapter 4, the [beta]-diketimine ligand was adapted, resulting in two separate classes of pro-ligands. The first, a 1,3,5-triazapentadiene, has had the central carbon replaced by nitrogen. The second, instead of having the typical methyl groups on the ligand backbone, has dialkylamino groups. In each instance, it was envisaged that the ligands would donate additional electron density, and bind more strongly to the metal centre in coordination complexes, when compared to the standard [beta]-diketiminate ligand class. Six separate heteroleptic magnesium(II) iodide complexes have been developed from these ligands, the majority of which show promise as precursors to low oxidation state magnesium complexes.Chapter 5 details several new secondary amines which have been produced as pro-ligands for low oxidation state main group chemistry. In addition, preliminary studies have shown that these ligands have potential in coordination chemistry.
Book Synopsis Beta -Diketiminate Ligand Supported Group 2 Metal Hydroxide, Halide, Oxygen Bridged Heterobimetallic and Heterotrimetallic Complexes by : Sharanappa Nembenna
Download or read book Beta -Diketiminate Ligand Supported Group 2 Metal Hydroxide, Halide, Oxygen Bridged Heterobimetallic and Heterotrimetallic Complexes written by Sharanappa Nembenna and published by . This book was released on 2007 with total page 196 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Β-diketiminate [Beta-diketiminate] Ligand Supported Group 2 Metal Hydroxide, Halide, Oxygen Bridged Heterobimetallic and Heterotrimetallic Complexes by : Sharanappa Nembenna
Download or read book Β-diketiminate [Beta-diketiminate] Ligand Supported Group 2 Metal Hydroxide, Halide, Oxygen Bridged Heterobimetallic and Heterotrimetallic Complexes written by Sharanappa Nembenna and published by . This book was released on 2007 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis, Structure, and Reactivity of Group 13 Diketiminate Complexes by : Baixin Qian
Download or read book Synthesis, Structure, and Reactivity of Group 13 Diketiminate Complexes written by Baixin Qian and published by . This book was released on 1999 with total page 362 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Ligands written by Paula Gawryszewska and published by Nova Science Publishers. This book was released on 2014 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: To meet the search for new therapeutic compounds this book summarises the research on biologically active organic molecules (chapters 1, 2 and 3), metal complexes with biological activity (chapter 4), and shows the possibilities for co-ordination chemistry in the planning of metal complexes with interesting properties for application (chapters 5, 6, 7, 8, and 9). It should be remembered that in the design of a new potentially active metallodrug, beyond the nature of the metal, the choice of appropriate ligands which affect the thermodynamic and kinetic stability, as well as the solubility and lipophilicity of the complexes is of paramount importance. The information contained in the book concerns: 1) the interactions involving the members of the Nuclear Receptor superfamily and their ligands; 2) the role of chemokine ligands and their receptors in normal and disease processes, and the emerging therapeutic approaches of using chemokine antagonists for appropriately targeted therapy; 3) the inhibition of alkaline phosphatases by calix[4]arenes functionalysed at the macrocyclic upper rim by one or two methylenebisphosphonic acid fragments; 4) the main biological applications, enzyme modelling and antiproliferative and antimicrobial activity of such scorpionate-type complexes, which are classified by ligand and also by transition metal; 5) the silver(I) discrete and polymeric coordination compounds bearing 1,3,5-triaza-7-phosphaadamantane or its derivatives towards engineering functional silver-organic frameworks (MOFs); 6) arylhydrazones of methylene active nitriles and their use as starting materials for the generation of new organic and coordination compounds; 7) amidophosphate ligands as promising sensitisers of lanthanide ions emission; 8) N-acetylsalicylhydrazidate as a versatile ligand for the synthesis of higher nuclearity metal complexes, which are illustrated herein along with their applications; 9) the chemistry and some applications of formazans which can be used for the simultaneous selective determination of several metal cations. All chapters were compiled by renowned scientists, providing both beginners in the field and advanced researchers with comprehensive information on the subject.
Book Synopsis Synthesis, Characterization and Reactivity Studies of Group 2, 3 and 4 Metal Complexes Bearing Chelating Amino Siloxide and Alkoxide Ligands by : Pengcheng Patrick Shao
Download or read book Synthesis, Characterization and Reactivity Studies of Group 2, 3 and 4 Metal Complexes Bearing Chelating Amino Siloxide and Alkoxide Ligands written by Pengcheng Patrick Shao and published by . This book was released on 1997 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Development of Bulky Dipyrromethene Complexes of Aluminum, Zinc and Rhodium by : Christopher G. Gianopoulos
Download or read book Development of Bulky Dipyrromethene Complexes of Aluminum, Zinc and Rhodium written by Christopher G. Gianopoulos and published by . This book was released on 2014 with total page 238 pages. Available in PDF, EPUB and Kindle. Book excerpt: The chemistry of dipyrromethene ligands is dominated by boron difluoride luminophores (BODIPY), which are commercially important laser dye materials and have also found application to imaging/staining biological samples. Despite the importance of BODIPY complexes, dipyrromethene complexes of the heavier group 13 elements are scarce. Our interest in bulky dipyrromethene ligands is based on analogy to popular ß-diketiminate ligands that have found use in stabilizing unusual metal complexes on the basis of steric protection. The preparation and characterization of aluminum, zinc and rhodium complexes of bulky dipyrromethene ligands is the subject of the following discourse. The preparation and characterization of aluminum alkyl, aryl and hydride complexes of 1,9-dimesityl-5-phenyldipyrromethene is reported in chapter two. The synthesis and characterization of a bimetallic aluminoxane with terminal hydride coligands is also reported. The preparation and characterization of dimethylaluminum complexes of 1,9-dimesityl-5-pentafluorophenyldipyrromethene and 1,9-dimesityl-5-(2'-pyridyl)dipyrromethene are also reported. These compounds have been characterized by NMR spectroscopy and X-ray crystallography. The structural data clearly demonstrate similarities and differences of the steric environment of dipyrromethene and ß-diketiminate ligands. The alkyl and aryl aluminum complexes are surprisingly robust and tolerate exposure to air, moisture and even silica gel chromatography. We have proposed that the stability of these compounds is due to kinetic stabilization afforded by the steric environment of the bulky dipyrromethene ligand. The preparation of aluminum complexes of 1,9-dimesityl-5-phenyldipyrromethene is extended in chapter 3. In this chapter, the preparation of aluminum complexes with halide, alkoxide and amido coligands is reported. These complexes were characterized by NMR spectroscopy and X-ray crystallography. The alkoxide and amido complexes were also evaluated for their ability to initiate the polymerization of e-caprolactone and preliminary results are discussed. Unfortunately, these aluminum complexes are poor catalysts for caprolactone polymerization, which only proceeds at elevated temperature. Furthermore, the aluminum catalysts are sensitive to impurities in the lactone monomer and catalysis was often found to halt after long reaction times. As mentioned previously, we became interested in the chemistry of aluminum complexes of dipyrromethene ligands based on analogy to ß-diketiminate ligands. ß-Diketiminate ligands have found use in stabilizing rare metal complexes, such as terminal imido complexes of aluminum. A major aim of our work with dipyrromethenes is to identify a system capable of stabilizing aluminum complexes with terminal divalent coligands such as imido or alkylidene ligands. In chapter 4, theoretical calculations performed at the DFT level are presented. The electronic structure of dipyrromethene aluminum complexes with terminal imido and alkylidene coligands was calculated as well as the thermochemical parameters of reactions to prepare such complexes. Synthetically viable substitutions were made in order to determine the effect of electronic perturbations (to the dipyrromethene or alkylidene coligand) on the stability of terminal alkylidene complexes of aluminum. The results of this chapter show that a terminal alkylidene of aluminum must be formed from an Al(I) precursor, rather than Al(III), and also that modification of the electronics of these systems has little effect on the stability of the resulting complexes. These results indicate that isolation of a stable, terminal alkylidene complex of aluminum will likely require kinetic stabilization of the reactive alkylidene moiety by use of steric bulk rather than stabilization through electronic modification to the system. Chapter 5 concerns the preparation and characterization of zinc halide, alkyl and alkoxide complexes of 1,9-dimesityl-5-phenyldipyrromethene. These compounds have been characterized by NMR spectroscopy and X-ray crystallography. The preparation of monomeric zinc alkoxides has been challenging and results to this aim are discussed at length. As an extension of the work reported in chapter 3, we have also explored the polymerization of e-caprolactone initiated by zinc alkoxide complexes and preliminary results will be discussed. In chapter 6 the preparation and characterization of rhodium(I) 1,5-cyclooctadiene (COD), carbon monoxide (CO) and arene complexes of 1,9-dimesityl-5-pentafluorophenyldipyrromethene are reported. These complexes were characterized by NMR spectroscopy and X-ray crystallography. Results from this chapter demonstrate the flexibility of the dipyrromethene ligand to accommodate square-planar coordination to rhodium(I). The preparation of low-coordinate rhodium complexes is also discussed. Chapter 7 reports the synthesis of Cr(TPP)Cl(THF), a component of the Coates system for carbonylation of epoxides, by a previously unreported method. Traditionally, Cr(TPP)Cl(THF) is prepared from divalent or zero-valent chromium precursors that are expensive, air-sensitive materials. Our method involves the use of inexpensive, air-stable trivalent chromium. Appendix 1 reports the synthesis and characterization of three compounds which were prepared as parts of side projects. The experimental details and crystal structures are reported, discussion is however kept to a minimum. The compounds presented in the appendix include nickel bromide and chromium chloride complexes of 1,9-dimesityl-5-phenyldipyrromethene and also a pseudo-octahedral homoleptic aluminum complex ligated by 2-(2'-pyridyl)pyrrole.
Book Synopsis Ligand Platforms in Homogenous Catalytic Reactions with Metals by : Ryohei Yamaguchi
Download or read book Ligand Platforms in Homogenous Catalytic Reactions with Metals written by Ryohei Yamaguchi and published by John Wiley & Sons. This book was released on 2014-11-17 with total page 358 pages. Available in PDF, EPUB and Kindle. Book excerpt: Serving as a user's manual for synthetic organic and catalytic chemists, this book guides chemists in the design and choice of ligands to catalyze organic reactions and apply the results for more efficient, green, and practical synthesis. • Focuses on the role of ligands in metal complexes that catalyze green organic transformations: a hot topic in the area of organic synthesis and green chemistry • Offers a comprehensive resource to help readers design and choose ligands and understand selectivity/reactivity characteristics • Addresses a gap by taking novel ligand approaches and including up-to-date discussion on hydrogen transfers and reactions • Presents important industrial perspective and provides rational explanations of ligand effects, impacts, and novelty
Book Synopsis Early Main Group Metal Catalysis by : Sjoerd Harder
Download or read book Early Main Group Metal Catalysis written by Sjoerd Harder and published by John Wiley & Sons. This book was released on 2020-04-06 with total page 400 pages. Available in PDF, EPUB and Kindle. Book excerpt: Early Main Group Metal Catalysis gives a comprehensive overview of catalytic reactions in the presence of group 1 and group 2 metals. Chapters are ordered to reaction type, contain educational elements and deal with concepts illustrated by examples that cover the main developments. After a short introduction on polar organometallic chemistry and synthesis of early main group metal complexes, a variety of catalytic reactions are described, e.g. polymerization of alkenes, hydroamination and phosphination reactions, hydrosilylation, hydroboration and hydrogenation catalysis, as well as enantioselective and Lewis-acid catalysis. The book addresses organic chemists and researchers in industry interested in the state-of-the-art and new possibilities of early main group metal catalysis as well as newcomers to the field. Written by a team of leaders in the field, it is a very welcome addition to the area of main group metal chemistry, and to the field of catalysis.
Book Synopsis Alkaline-Earth Metal Compounds by : Sjoerd Harder
Download or read book Alkaline-Earth Metal Compounds written by Sjoerd Harder and published by Springer. This book was released on 2013-07-20 with total page 282 pages. Available in PDF, EPUB and Kindle. Book excerpt: The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics in pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors.
Book Synopsis Ligand-based Reduction Chemistry of F Element Complexes by : Kevin A. Miller
Download or read book Ligand-based Reduction Chemistry of F Element Complexes written by Kevin A. Miller and published by . This book was released on 2008 with total page 428 pages. Available in PDF, EPUB and Kindle. Book excerpt: Chapter 9 describes reactivity studies of (C5Me5)U[mu-eta 5:eta1:eta1-C5 Me3(CH2)2](mu-H)2U(C 5Me5)2. This complex is a reductant in its own right and provides another option in reductive actinide chemistry.
Book Synopsis Synthesis, Structures, and Reactivity of Heavy Alkaline-earth Complexes with Sterically Bulky Ligands by : Melanie Jean Harvey
Download or read book Synthesis, Structures, and Reactivity of Heavy Alkaline-earth Complexes with Sterically Bulky Ligands written by Melanie Jean Harvey and published by . This book was released on 2000 with total page 322 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis The Synthesis and Structural Characterization of Main Group and Transition Metal Complexes Supported by Nitrogen Based Ligands by :
Download or read book The Synthesis and Structural Characterization of Main Group and Transition Metal Complexes Supported by Nitrogen Based Ligands written by and published by . This book was released on 2001 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Nitrogen based monodentate and bidentate chelating ligands have captured a significant interest due to their ability to coordinate to a wide variety of elements. The â-diketimine, â-ketoiminato, formamidine, pyridineselenolate, and pyrazinecarboxamide ligands have all been employed in this study to further investigate the coordination preferences among main group and transition metals. Steric and electronic properties of these ligands can easily be altered by manipulating the substituents attached, thus leading to predictable structures with potential for many useful and significant applications. Investigations have shown that temperature, solvent, and metal halide employed are all key factors in the reaction outcomes. All of the complexes obtained throughout these studies have been characterized by X-ray crystallography along with other spectroscopic techniques, including NMR, IR, UV/Vis, and M/S. â-diketiminato ligands, [{N(R)C(Me)}2C(H)] where R = Dipp, Mes, commonly referred to as nacnac, have played an important role in the synthesis of novel pnictogenium complexes. Results show that through manipulation of the halide precursor, reaction stoichiometry, and the R substituent on the nacnac both N, N'- and N, C'-metal chelated complexes can be achieved. Additionally, â-ketiminato ligands, [RN(H)(C(Me))2C(Me)=O] where R = Dipp, and [RN(H)C(Me)CHC(Me)=O] where R = C2H4NEt2, have been studied. Both ligands were investigated with a range of d and p block metal halides and alkyls in order to compare and contrast the bulky, flexible, and even multi-dentate nature of each ligand. The preferred metal geometry remains constant for products with either ligand, but the steric protection offered by the individual ligands governs the nuclearity of the products, ranging from tetrameric cages to simple adducts. The formamidinate ligand, [RN(H)C(H)NR] where R = Dipp, was employed in synthesizing several aluminum and zinc complexes. In addition to their numerous applications as cata.
Book Synopsis The Group 13 Metals Aluminium, Gallium, Indium and Thallium by : Simon Aldridge
Download or read book The Group 13 Metals Aluminium, Gallium, Indium and Thallium written by Simon Aldridge and published by John Wiley & Sons. This book was released on 2011-02-10 with total page 990 pages. Available in PDF, EPUB and Kindle. Book excerpt: The last two decades have seen a renaissance in interest in the chemistry of the main group elements. In particular research on the metals of group 13 (aluminium, gallium, indium and thallium) has led to the synthesis and isolation of some very novel and unusual molecules, with implications for organometallic synthesis, new materials development, and with biological, medical and, environmental relevance. The Group 13 Metals Aluminium, Gallium, Indium and Thallium aims to cover new facts, developments and applications in the context of more general patterns of physical and chemical behaviour. Particular attention is paid to the main growth areas, including the chemistry of lower formal oxidation states, cluster chemistry, the investigation of solid oxides and hydroxides, advances in the formation of III-V and related compounds, the biological significance of Group 13 metal complexes, and the growing importance of the metals and their compounds in the mediation of organic reactions. Chapters cover: general features of the group 13 elements group 13 metals in the +3 oxidation state: simple inorganic compounds formal oxidation state +3: organometallic chemistry formal oxidation state +2: metal-metal bonded vs. mononuclear derivatives group 13 metals in the +1 oxidation state mixed or intermediate valence group 13 metal compounds aluminium and gallium clusters: metalloid clusters and their relation to the bulk phases, to naked clusters, and to nanoscaled materials simple and mixed metal oxides and hydroxides: solids with extended structures of different dimensionalities and porosities coordination and solution chemistry of the metals: biological, medical and, environmental relevance III-V and related semiconductor materials group 13 metal-mediated organic reactions The Group 13 Metals Aluminium, Gallium, Indium and Thallium provides a detailed, wide-ranging, and up-to-date review of the chemistry of this important group of metals. It will find a place on the bookshelves of practitioners, researchers and students working in inorganic, organometallic, and materials chemistry.
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