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Book Reactions of Coordinated Ligands

Download or read book Reactions of Coordinated Ligands written by P.S. Braterman and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 419 pages. Available in PDF, EPUB and Kindle. Book excerpt: This, the second and final volume of Reactions of Coordinated Ligands, describes the chemistry of ligands bound through non-carbon atoms, and of coordinated carbon dioxide. As before, emphasis is on the underlying mechanisms, which provide a unity of understanding for superficially disparate processes. The wide range of topics covered illustrates well both the versatility and the usefulness of coordination chemistry in the controlled activation of ligands. Looking to the future, carbon dioxide is the feedstock of last resort. The homogeneous reduction of dinitrogen to ammonia now seems unlikely to replace the Haber process, but solution reactions also lead to more complex, varied, and valuable products. Nitrogen monoxide, a "non innocent" ligand, impinges as pollutant and reagent. Its rich chemistry stems from its linked roles as three-electron donor, and as extremely powerful -acceptor. In the hydrolysis and condensation of complexed amides, esters etc. , metals act both as templates and as tunable and poly functional Lewis acids. Here the control of hydrophobic and steric interactions begins to model the subtle mechanisms of biological specificity. Finally, phosphorus and sulfur are imporant both as ligand atoms in themselves, and as anchors for other functionalities. I would like to thank all those who have been involved in the writing and production of this work, and also my colleagues old and new, at Glasgow and the University of North Texas, for their support. Paul S. Braterman v CONTENTS 1. Reactions of Coordinated Carbon Dioxide 1 J. D. Miller 1.

Book The Organometallic Chemistry of the Transition Metals

Download or read book The Organometallic Chemistry of the Transition Metals written by Robert H. Crabtree and published by John Wiley & Sons. This book was released on 2005-06-14 with total page 600 pages. Available in PDF, EPUB and Kindle. Book excerpt: Fully updated and expanded to reflect recent advances, this Fourth Edition of the classic text provides students and professional chemists with an excellent introduction to the principles and general properties of organometallic compounds, as well as including practical information on reaction mechanisms and detailed descriptions of contemporary applications.

Book Ligand Substitution Processes

Download or read book Ligand Substitution Processes written by Cooper Harold Langford and published by . This book was released on 1966 with total page 130 pages. Available in PDF, EPUB and Kindle. Book excerpt: The subject of the mechanistic study of ligand substitution reactions is currently undergoing an exciting growth. New fast-reaction techniques have removed the upper limit on rates that can be measured, and extension to less familiar central metal atoms has begun in earnest. This might seem the wrong moment for review of the field. As yet, definitive treatment is possible only for those complexes involving monodentate ligands with cobalt(III) and platinurn(II). But, because information is so extensive for these systems, it is clear that they are functioning as models from which concepts and experiments are generated for application over the fast-growing range of the subject. We believe that this is an important moment to reopen debate on fundamentals so that concepts will be most felicitously formulated to aid growth of understanding. This monograph is centrally concerned with three aspects of those fundamentals. We have attempted to develop an approach to classification of ligand substitution reactions that is adapted to what seem to have emerged as the characteristic features of these reactions and is susceptible to operational tests. (We do recognize that any such scheme of ideas is necessarily obsolescent once it is formulated since new experiments will certainly follow immediately.) We have tried to evaluate the basis for making generalizations about ligand substitution processes and to formulate tests to show whether new reactions fall within familiar patterns. Finally, we have sought to base the models of ligand substitution processes in the language of molecular-orbital theory. We believe that MO theory is most useful, because it may be used to correlate rate data on complexes with the extensive information available from spectral and magnetic studies, yet differs from crystal-field theory in providing a natural place for consideration of the bonding electrons, which must be a principal determinant of reaction processes. To keep this essay within bounds, we assume familiarity with the elements of experimental kinetics, transition-state theory, and the simple molecular-orbital theory of complexes. Introductory physical chemistry, some familiarity with the study of reaction mechanisms, and mastery of one of the qualitative treatments of MO theory as applied to transition-metal complexes should provide sufficient background. Thus, we hope that this book will be useful to students, relatively early in their careers, who wish to explore this field.

Book Dissertation Abstracts International

Download or read book Dissertation Abstracts International written by and published by . This book was released on 2007 with total page 924 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book A Study of Ligand Substitution Reactions in the Five Coordinate Complexes   Cu  TREN OH2 2   Cu  Me6 TREN OH2 2  and  Cu  Me6 TREN OH

Download or read book A Study of Ligand Substitution Reactions in the Five Coordinate Complexes Cu TREN OH2 2 Cu Me6 TREN OH2 2 and Cu Me6 TREN OH written by Peter Ralph Collins and published by . This book was released on 1979 with total page 274 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Mechanisms of Inorganic and Organometallic Reactions

Download or read book Mechanisms of Inorganic and Organometallic Reactions written by M.V. Twigg and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 458 pages. Available in PDF, EPUB and Kindle. Book excerpt: This series provides a continuing critical review of the literature concerned with mechanistic aspects of inorganic and organometallic reactions in solu tion, with coverage over the whole area being complete in each volume. The format of this second volume is very similar to that of the first, with material arranged according to reaction type and compound type along generally accepted lines. Papers discussed are selected on the basis of relevance to the elucidation of reaction mechanisms but may also include results of a nonkinetic nature, such as stereochemical studies and product ratios, when useful mechanistic information can be deduced. In this volume extra space has been given to areas concerned with electron transfer processes and substitution reactions of inert complexes, and to improve convenience for the reader the text has been further divided to form three additional chapters. Electron transfer processes are discussed in three chapters: "General and Theoretical," "Reactions between Two Complexes," and "Metal-Ligand Redox Reactions," while six chapters are concerned with substitution and related reactions. Here reactions of inert chromium and cobalt complexes are discussed in separate chapters. The period of literature coverage is January 1981 through June 1982 inclusive and in a few instances, where delays in delivery of journals have been encountered, the issues not covered will be included in the next volume.

Book Reaction Mechanisms of Metal Complexes

Download or read book Reaction Mechanisms of Metal Complexes written by R W Hay and published by Elsevier. This book was released on 2000-03-01 with total page 177 pages. Available in PDF, EPUB and Kindle. Book excerpt: This text provides a general background as a course module in the area of inorganic reaction mechanisms, suitable for advanced undergraduate and postgraduate study and/or research. The topic has important research applications in the metallurgical industry and is of interest in the science of biochemistry, biology, organic, inorganic and bioinorganic chemistry. In addition to coverage of substitution reactions in four-, five- and six-coordinate complexes, the book contains further chapters devoted to isomerization and racemization reactions, to the general field of redox reactions, and to the reactions of coordinated ligands. It is relevant in other fields such as organic, bioinorganic and biological chemistry, providing a bridge to organic reaction mechanisms. The book also contains a chapter on the kinetic background to the subject with many illustrative examples which should prove useful to those beginning research. Provides a general background as a course module in the area of inorganic reaction mechanisms, which has important research applications in the metallurgical industry Contains further chapters devoted to isomerization and racemization reactions, to the general field of redox reactions, and to the reactions of coordinated ligands

Book Organometallic Pincer Chemistry

Download or read book Organometallic Pincer Chemistry written by Gerard van Koten and published by Springer. This book was released on 2012-09-17 with total page 363 pages. Available in PDF, EPUB and Kindle. Book excerpt: Gerard van Koten: The Mono-anionic ECE-Pincer Ligand - a Versatile Privileged Ligand Platform: General Considerations.- Elena Poverenov, David Milstein: Non-Innocent Behavior of PCP and PCN Pincer Ligands of Late Metal Complexes.- Dean M. Roddick: Tuning of PCP Pincer Ligand Electronic and Steric Properties.- Gemma R. Freeman, J. A. Gareth Williams: Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and Luminescence.- Davit Zargarian, Annie Castonguay, Denis M. Spasyuk: ECE-Type Pincer Complexes of Nickel.- Roman Jambor and Libor Dostál: The Chemistry of Pincer Complexes of 13 - 15 Main Group Elements.- Kálmán J. Szabo: Pincer Complexes as Catalysts in Organic Chemistry.- Jun-ichi Ito and Hisao Nishiyama: Optically Active Bis(oxazolinyl)phenyl Metal Complexes as Multi-potent Catalysts.- Anthony St. John, Karen I. Goldberg, and D. Michael Heinekey: Pincer Complexes as Catalysts for Amine Borane Dehydrogenation.- Dmitri Gelman and Ronit Romm: PC(sp3)P Transition Metal Pincer Complexes: Properties and Catalytic Applications.- Jennifer Hawk and Steve Craig: Physical Applications of Pincer Complexes.

Book The Stille Reaction

    Book Details:
  • Author : Vittorio Farina
  • Publisher : John Wiley & Sons
  • Release : 1998-09-18
  • ISBN : 9780471312734
  • Pages : 676 pages

Download or read book The Stille Reaction written by Vittorio Farina and published by John Wiley & Sons. This book was released on 1998-09-18 with total page 676 pages. Available in PDF, EPUB and Kindle. Book excerpt: Die Stille-Reaktion ist eine der sehr wenigen Reaktionen, in denen unter milden Bedingungen Kohlenstoff-Kohlenstoff-Bindungen geknüpft werden können. Man verwendet die Reaktion häufig in der Synthese komplizierter Moleküle zur Verknüpfung größerer Molekülbausteine. Die Autoren diskutieren vom präparativen Standpunkt aus Grenzen, Einflüsse, strukturelle Effekte und die Wahl der geeigneten Reaktionsbedingungen. Mit ausführlichen Vorschriften und vielen Beispielen. (11/98)

Book Design  Synthesis  and Reactivity of Bimetallic Complexes of Dimethylplatinum II  Containing Ditopic Ligands

Download or read book Design Synthesis and Reactivity of Bimetallic Complexes of Dimethylplatinum II Containing Ditopic Ligands written by Matthew S. McCready and published by . This book was released on 2015 with total page 658 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis describes a study of monometallic and bimetallic dimethylplatinum(II) complexes containing ditopic nitrogen donor ligands. This work details the design and synthesis of side-to-side and cofacial arranged ligands and their respective coordination chemistry. The study of the synthesis, characterization and reaction mechanisms of the various dimethylplatinum(II) complexes is outlined in detail with special emphasis focused on the reactivity of the complexes towards oxidative addition. The ditopic ligand 6-dppd, 1,4-di(2-pyridyl)-5,6,7,8,9,10- hexahydrocycloocta[d]pyridazine, was observed to coordinate only a single equivalent of a platinum(II) center. The inability to coordinate a second equivalent, even through an assisted bridging atom, is presumed to be due to a steric clash between the free pyridyl group and the cyclooctyl backbone. In attempts to make heterobimetallic complexes of 6-dppd, the complex [PtMe2(6-dppd)] was observed to react preferentially with mercuric halides by oxidative addition rather than coordination of the mercuric salt in the second coordination site giving complexes [PtXMe2(HgX)(6-dppd)] where X = Br, Cl, OAc. This indicates that the platinum center is actually a better nucleophile than the free pyridyl nitrogen atom. The oxidative addition of solvent dichloromethane was also observed showing the enhancedreactivity of [PtMe2(6-dppd)]. Finally, [PtMe2(6-dppd)] was treated with DCl at low temperature to give the deuteridoplatinum(IV) complex. The deuteridoplatinum(IV) complex reductively eliminates methane in solution and extensive H/D exchange occurs into the CH4 product at low temperature indicating very easy reversibility of the exchange between hydridomethylplatinum(IV) and methaneplatinum(II) complexes. The abstraction of a chloride ligand from [PtClMe(6-dppd)] led to the formation of a complex dimer structure endo, endo-[Pt2Me2(?2-?3-6-dppd)2][OTf]2. This process allowed for the formation of a bimetallic platinum(II) complex which retained the initial stereochemistry. The protonolysis of [PtMe2(6-dppd)] with one equivalent of HOTf led to the generation of methane gas and the concomitant formation of both endo, endo-[Pt2Me2(?2-?3-6-dppd)2][OTf]2 and exo, exo-[Pt2Me2(?2-?3-6-dppd)2][OTf]2. The structures of the exo isomeric clamshell dimers appeared much less sterically hindered in the solid state and were observed experimentally and computationally to be the thermodynamically preferred isomers. The mechanism, selectivity and reversibility of this isomerism process was explored in detail. The reactions of [PtMe2(6-dppd)] with alkyl bromides RCH2Br, which possess hydrogen bonding functionality, result in the formation of stable organoplatinum(IV) complexes capable of forming supramolecular structure via hydrogen bonding. Both intra and inter molecular hydrogen bonding is observed in the formation of supramolecular architectures which self-assemble in the solid state through additional?-stacking and weak secondary interactions. The new anthracene derived ditopic ligands, bpad = N1,N8-bis(pyridin-2- ylmethylene)anthracene-1,8-diamine and adpa = (N, N)-4,4'-(anthracene-1,8-diylbis(ethyne- 2,1-diyl))-bis(N-(pyridin-2-ylmethylene)aniline) were prepared, characterized and used to coordinate dimethylplatinum(II) centers giving cofacial bimetallic complexes of dimethylplatinum(II). [Pt2Me4(bpad)] was shown to degrade over time in solution through a proposed metalation event involving the anthracene backbone. The oxidative addition of a variety of substrates was performed using [Pt2Me4(adpa)] giving stable diplatinum(IV) complexes as characterized by 1H NMR spectroscopy. The new xanthene derived ditopic ligands, ppxda = 2,7-di-tert-butyl-9,9-dimethyl-N4,N5-bis(4-(pyridin-2- ylmethyleneamino)phenyl)-xanthene-4,5-dicarboxamide and pmxda = 2,7-di-tert-butyl-9,9- dimethyl-bis(pyridine-2-ylmethylene)-9H-xanthene-4,5-diamine were prepared characterized and used to ligate two equivalents of a dimethylplatinum(II) center. Diplatinum complexes of both ligands were shown to easily undergo oxidative addition to give the corresponding diplatinum(IV) complexes which adopt the anti orientation. The syn alignment of metal centers was accessible through the abstraction of halides ligands and incorporation of bridging groups as is the case for the pyrazine bridged bimetallic platinum complex [Pt2Me6(C4H4N2)(pmxda)][OSO2CF3]2.

Book Inorganic Chemistry

Download or read book Inorganic Chemistry written by Egon Wiberg and published by Academic Press. This book was released on 2001 with total page 1958 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book A Textbook of Inorganic Chemistry     Volume 1

Download or read book A Textbook of Inorganic Chemistry Volume 1 written by Mandeep Dalal and published by Dalal Institute. This book was released on 2017-01-01 with total page 480 pages. Available in PDF, EPUB and Kindle. Book excerpt: An advanced-level textbook of inorganic chemistry for the graduate (B.Sc) and postgraduate (M.Sc) students of Indian and foreign universities. This book is a part of four volume series, entitled "A Textbook of Inorganic Chemistry – Volume I, II, III, IV". CONTENTS: Chapter 1. Stereochemistry and Bonding in Main Group Compounds: VSEPR theory, dπ -pπ bonds, Bent rule and energetic of hybridization. Chapter 2. Metal-Ligand Equilibria in Solution: Stepwise and overall formation constants and their interactions, Trends in stepwise constants, Factors affecting stability of metal complexes with reference to the nature of metal ion and ligand, Chelate effect and its thermodynamic origin, Determination of binary formation constants by pH-metry and spectrophotometry. Chapter 3. Reaction Mechanism of Transition Metal Complexes – I: Inert and labile complexes, Mechanisms for ligand replacement reactions, Formation of complexes from aquo ions, Ligand displacement reactions in octahedral complexes- acid hydrolysis, Base hydrolysis, Racemization of tris chelate complexes, Electrophilic attack on ligands. Chapter 4. Reaction Mechanism of Transition Metal Complexes – II: Mechanism of ligand displacement reactions in square planar complexes, The trans effect, Theories of trans effect, Mechanism of electron transfer reactions – types; Outer sphere electron transfer mechanism and inner sphere electron transfer mechanism, Electron exchange. Chapter 5. Isopoly and Heteropoly Acids and Salts: Isopoly and Heteropoly acids and salts of Mo and W: structures of isopoly and heteropoly anions. Chapter 6. Crystal Structures: Structures of some binary and ternary compounds such as fluorite, antifluorite, rutile, antirutile, crystobalite, layer lattices- CdI2, BiI3; ReO3, Mn2O3, corundum, pervoskite, Ilmenite and Calcite. Chapter 7. Metal-Ligand Bonding: Limitation of crystal field theory, Molecular orbital theory, octahedral, tetrahedral or square planar complexes, π-bonding and molecular orbital theory. Chapter 8. Electronic Spectra of Transition Metal Complexes: Spectroscopic ground states, Correlation and spin-orbit coupling in free ions for Ist series of transition metals, Orgel and Tanabe-Sugano diagrams for transition metal complexes (d1 – d9 states), Calculation of Dq, B and β parameters, Effect of distortion on the d-orbital energy levels, Structural evidence from electronic spectrum, John-Tellar effect, Spectrochemical and nephalauxetic series, Charge transfer spectra, Electronic spectra of molecular addition compounds. Chapter 9. Magantic Properties of Transition Metal Complexes: Elementary theory of magneto - chemistry, Guoy’s method for determination of magnetic susceptibility, Calculation of magnetic moments, Magnetic properties of free ions, Orbital contribution, effect of ligand-field, Application of magneto-chemistry in structure determination, Magnetic exchange coupling and spin state cross over. Chapter 10. Metal Clusters: Structure and bonding in higher boranes, Wade’s rules, Carboranes, Metal Carbonyl Clusters - Low Nuclearity Carbonyl Clusters, Total Electron Count (TEC). Chapter 11. Metal-π Complexes: Metal carbonyls, structure and bonding, Vibrational spectra of metal carbonyls for bonding and structure elucidation, Important reactions of metal carbonyls; Preparation, bonding, structure and important reactions of transition metal nitrosyl, dinitrogen and dioxygen complexes; Tertiary phosphine as ligand.

Book The Chemistry of Pincer Compounds

Download or read book The Chemistry of Pincer Compounds written by David Morales-Morales and published by Elsevier. This book was released on 2011-08-11 with total page 467 pages. Available in PDF, EPUB and Kindle. Book excerpt: Pincer complexes are formed by the binding of a chemical structure to a metal atom with at least one carbon-metal bond. Usually the metal atom has three bonds to a chemical backbone, enclosing the atom like a pincer. The resulting structure protects the metal atom and gives it unique properties.The last decade has witnessed the continuous growth in the development of pincer complexes. These species have passed from being curiosity compounds to chemical chameleons able to perform a wide variety of applications. Their unique metal bound structures provide some of the most active catalysts yet known for organic transformations involving the activation of bonds. The Chemistry of Pincer Compounds details use of pincer compounds including homogeneous catalysis, enantioselective organic transformations, the activation of strong bonds, the biological importance of pincer compounds as potential therapeutic or pharmaceutical agents, dendrimeric and supported materials. * Describes the chemistry and applications of this important class of organometallic and coordination compounds* Covers the areas in which pincer complexes have had an impact* Includes information on more recent and interesting pincer compounds not just those that are well-known