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Metal Ligand Multiple Bonds In Nickel Complexes Supported By Chelating Bisphosphine Ligands
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Book Synopsis Metal-ligand Multiple Bonds in Nickel Complexes Supported by Chelating Bisphosphine Ligands by : Vlad Mihai Iluc
Download or read book Metal-ligand Multiple Bonds in Nickel Complexes Supported by Chelating Bisphosphine Ligands written by Vlad Mihai Iluc and published by . This book was released on 2009 with total page 550 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Metal-Ligand Multiple Bonds by : William A. Nugent
Download or read book Metal-Ligand Multiple Bonds written by William A. Nugent and published by Wiley-Interscience. This book was released on 1988-11-14 with total page 360 pages. Available in PDF, EPUB and Kindle. Book excerpt: The only comprehensive one-volume text/reference on metal-ligand multiple bonds. Stresses the unified nature of the field and includes handy new tabulations of data. The flow within each subtopic is oxygen to nitrogen to carbon. Coverage is up-to-date--virtually every subtopic leads to interesting questions for future research. Presents information otherwise scattered through hundreds of publications.
Book Synopsis Syntheses, Structures and Reactivity of the Group 6 and 7 Metal Complexes Containing Chelating Nitrogen Donor Ligands and Metal-Ligand Multiple Bonds by : 李富華
Download or read book Syntheses, Structures and Reactivity of the Group 6 and 7 Metal Complexes Containing Chelating Nitrogen Donor Ligands and Metal-Ligand Multiple Bonds written by 李富華 and published by Open Dissertation Press. This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Syntheses, Structures and Reactivity of the Group 6 and 7 Metal Complexes Containing Chelating Nitrogen Donor Ligands and Metal-ligand Multiple Bonds" by 李富華, Fu-wa, Lee, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled "SYNTHESES, STRUCTURES AND REACTIVITY OF THE GROUP 6 AND 7 METAL COMPLEXES CONTAINING CHELATING NITROGEN DONOR LIGANDS AND METAL-LIGAND MULTIPLE BONDS" submitted by Lee Fu Wa for the degree of Doctor of Philosophy at the University of Hong Kong in September, 1997. ____________________________________________________________________ [Cr(CRMe )Cl ] (CRMe =meso-2,3,7,11,12-pentamethyl-3,7,11,17- 3 2 3 2+ tetraazabicyclo[11.3.1]-heptadeca-1(17),13,15-triene), [Cr(CRMe )Cl(H O)], 3 2 2+ + [Cr(CRMe )Cl(CH CN)] and [Cr(CRMe )(N )(OH)] are prepared. Upon addition 3 3 3 3 2+ 2+ of PhI=O to solutions of [Cr(CRMe )Cl(CH CN)] and [Cr(CRMe )Cl(H O)] 3 3 3 2 respectively in CH CN, the UV-visible absorption spectra of the two mixtures show similar isosbestic spectral changes attributed to the formation of V 2+ [Cr (CRMe )Cl(O)] . Addition of PhP causes the immediate recovery of 3 3 2+ [Cr(CRMe )Cl(CH CN)] as the isosbestic changes are reversed. Irradiation of 3 3 [Cr(CRMe )(N )(OH)] in acetonitrile with UV-visible light gives an azide-free 3 3 product, the FAB-MS of which shows a molecular ion peak indicative of V + + ([Cr (CRMe )(N)]ClO ). The UV-visible spectra of [Cr(CRMe )Cl ], 3 4 3 2 2+ 2+ [Cr(CRMe )Cl(H O)] and [Cr(CRMe )Cl(CH CN)] measured in water are 3 2 3 3 3+ similar to that of [Cr(CRMe )(H O) ] . Results from the conductivity measurement 3 2 2 + 2+ show that in water, [Cr(CRMe )Cl ], [Cr(CRMe )Cl(H O)] and 3 2 3 2 2+ [Cr(CRMe )Cl(CH CN)] behave as 3:1 electrolytes. The species which exists in 3 3 3+ water is likely to be the di-aquo complex [Cr(CRMe )(H O) ] . 3 2 2 2+ 2+ [Cr(CRMe )Cl(H O)] and [Cr(CRMe )Cl(CH CN)] are both found to give a 3 2 3 3 reversible oxidation couple at +1.11 V vs. SCE in aqueous solutions at pH=1 which is assigned to Cr(III)/(IV). iii t + The bis(imido) complexes [(TACN)M(N Bu) Cl] (M=Cr, Mo; TACN=1,4,7-triazacyclononane) and their 1,4,7-trimethyl derivatives are prepared, the crystal structures of which reveal the trans influence of the imido group. These 0 +/0 d species display a quasi-reversible couple at potentials 0.86 - 1.20 V vs. Cp Fe in acetonitrile assignable to a imido ligand-centred oxidation. (Me TACN)Mo(CO), 1,4,7-Tri((S)-2-methylbutyl)-1,4,7-triazacyclononane 3 3 * * * (L ) and L Mo(CO) are synthesized. (Me TACN)Mo(CO) and L Mo(CO) show 3 3 3 3 +/0 reversible oxidation couples at -0.26 V and -0.24 V vs. Cp Fe in CH CN 2 3 I/0 respectively which are assigned to Mo . The comparable electronic effect of * Me TACN and L in this system is therefore implied. 2+ [(Me TACN) Mn (μ-O)(μ-OCOCH ) ] is prepared and found to mediate 3 2 2 3 2 aziridination of styrene, methylstyrene, cis- and trans-stilbene, 1,1-diphenylethene and norbornene by PhI=NTs in CH Cl at 25 C. The nitrene transfer to cis- and 2 2 trans-stilbene is found to be stereoselective to exclusively give the trans-aziridine product. + + [(Me TACN)(CO) M CPh] (M=Mo, W) and [(TACN)(CO) Mo CPh] 3 2 2 are prepared. [(Me TACN)(CO) M CPh] (M=Mo, W) exhibit a reversible 3 2 +/0 reduction couple at -2.15 V vs Fe Cp and an irreversible wave at 0.77 V vs +/0 Fe Cp, which are ascribed to a reduction centred at the phenyl ring and oxidation of the terminal CO respectively. Treatment of Cl(
Book Synopsis Syntheses, Structures and Reactivity of the Group 6 and 7 Metal Complexes Containing Chelating Nitrogen Donor Ligands and Metal-ligand Multiple Bonds by : Fu-wa Lee
Download or read book Syntheses, Structures and Reactivity of the Group 6 and 7 Metal Complexes Containing Chelating Nitrogen Donor Ligands and Metal-ligand Multiple Bonds written by Fu-wa Lee and published by . This book was released on 1997 with total page 504 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Metal–Ligand Bonding written by E A Moore and published by Royal Society of Chemistry. This book was released on 2019-05-02 with total page 116 pages. Available in PDF, EPUB and Kindle. Book excerpt: To appreciate the chemistry and physical properties of complexes of the transition series, an understanding of metal-ligand interactions applied to complexes of the d-block is needed. Metal Ligand Bonding aims to provide this through an accessible, detailed, non-mathematical approach. Initial chapters detail the crystal-field model, using it to describe the use of magnetic measurements to distinguish complexes with different electronic configurations and geometries. Subsequent chapters look at the molecular orbital theory of transition metal complexes using a pictorial approach. Bonding in octahedral complexes is explored and electronic spectra and magnetic properties are given extensive coverage. The material addressed in this book forms the foundation of undergraduate lecture courses on d-block chemistry and facilitates learning through various key features, including: full colour diagrams; in-text questions with answers; revision exercises and clearly defined learning outcomes to encourage a reflective approach to study; an associated website; and experimental data and observations from everyday life. A basic knowledge of atomic and molecular orbitals as applied to main group elements is assumed.
Book Synopsis Metal-ligand Multiple Bonds as Single Atom Sources for the Assembly of New Ligands by : Jorge L. Martinez (Chemist)
Download or read book Metal-ligand Multiple Bonds as Single Atom Sources for the Assembly of New Ligands written by Jorge L. Martinez (Chemist) and published by . This book was released on 2020 with total page 224 pages. Available in PDF, EPUB and Kindle. Book excerpt: Atom transfer reactions such as HAT (hydrogen atom transfer) and OAT (oxygen atom transfer) offer a method for efficient bond formation in a single step. Extending this concept, this single atom delivery also has the potential to provide an effective route to otherwise inaccessible ligands. In this work, we investigate the utility of the tris(carbene)borate iron(IV) nitride, PhB(iPr2Im)3Fe≡N, as a viable nitrogen atom source for the assembly of new ligands. In one embodiment of this approach, an unusual carbon atom transfer reaction leads to the assembly of a C≡N− ligand when two equivalents of bis(diisopropylamino)cyclopropenylidene (BAC) carbene are added to PhB(iPr2Im)3Fe≡N. This strategy is extended to access of the elusive gas molecule, P≡N, which is assembled by using (N3N)Mo≡P (N3N = [N(CH2CH2NSiMe3)3]3−) and PhB(iPr2Im)3Fe≡N as P- and N-atom sources, respectively. These are the first structurally characterized compounds with this unique ligand. Photoisomerization of the P≡N ligand is observed in the solid-state and trapping of the N≡P linkage isomer reveals the fluxionality of this ligand in solution. Additionally, the bis(carbene)borate ligand framework is also explored as supporting ligand for the development of new metal-ligand multiply bonded complexes with the first structural characterization of an Fe(VI) compound, the highest oxidation state of iron, being achieved.
Book Synopsis Synthesis of Group 9 and 10 Metal Complexes Supported by Chelating Nitrogen-based Ligands and Mechanistic Studies of Their Role in Catalytic Transformations by : Jennifer Lauren McBee
Download or read book Synthesis of Group 9 and 10 Metal Complexes Supported by Chelating Nitrogen-based Ligands and Mechanistic Studies of Their Role in Catalytic Transformations written by Jennifer Lauren McBee and published by . This book was released on 2009 with total page 840 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Metal-ligand Multiple Bonds in Organometallic Complexes Containing Triamidoamine Ligand Systems by : Joel Stephen Freundlich
Download or read book Metal-ligand Multiple Bonds in Organometallic Complexes Containing Triamidoamine Ligand Systems written by Joel Stephen Freundlich and published by . This book was released on 1996 with total page 238 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Ligand Design in Metal Chemistry by : Mark Stradiotto
Download or read book Ligand Design in Metal Chemistry written by Mark Stradiotto and published by John Wiley & Sons. This book was released on 2016-09-01 with total page 448 pages. Available in PDF, EPUB and Kindle. Book excerpt: The design of ancillary ligands used to modify the structural and reactivity properties of metal complexes has evolved into a rapidly expanding sub-discipline in inorganic and organometallic chemistry. Ancillary ligand design has figured directly in the discovery of new bonding motifs and stoichiometric reactivity, as well as in the development of new catalytic protocols that have had widespread positive impact on chemical synthesis on benchtop and industrial scales. Ligand Design in Metal Chemistry presents a collection of cutting-edge contributions from leaders in the field of ligand design, encompassing a broad spectrum of ancillary ligand classes and reactivity applications. Topics covered include: Key concepts in ligand design Redox non-innocent ligands Ligands for selective alkene metathesis Ligands in cross-coupling Ligand design in polymerization Ligand design in modern lanthanide chemistry Cooperative metal-ligand reactivity P,N Ligands for enantioselective hydrogenation Spiro-cyclic ligands in asymmetric catalysis This book will be a valuable reference for academic researchers and industry practitioners working in the field of ligand design, as well as those who work in the many areas in which the impact of ancillary ligand design has proven significant, for example synthetic organic chemistry, catalysis, medicinal chemistry, polymer science and materials chemistry.
Book Synopsis Metal-ligand Multiple Bonds by : Tony Stüker
Download or read book Metal-ligand Multiple Bonds written by Tony Stüker and published by . This book was released on 2021 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Metal-ligand ''multiple'' Bonding by :
Download or read book Metal-ligand ''multiple'' Bonding written by and published by . This book was released on 1997 with total page 17 pages. Available in PDF, EPUB and Kindle. Book excerpt: This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The goal of this project has been to extend the understanding of the nature of interactions between f-metals and first row elements (important both in natural systems and in ceramics), as well as providing important new information regarding basic differences in the chemical nature of d- and f-metals. By developing preparative routes to novel classes of early actinide and lanthanide complexes in which metal-ligand bonding is formally unsaturated, this project has provided the means to study orbital interactions and charge distribution in these species by physical, chemical, and theoretical means. Evaluation of the physical and chemical characteristics of these species is providing dramatic evidence for the involvement of valence metal orbitals [nf and (n+1)d] in bonding, and is yielding new insights into the factors influencing stability of related species.
Book Synopsis Theoretical Studies of Transition Metal-ligand Multiple Bond Complexes by : Paul Dermot Lyne
Download or read book Theoretical Studies of Transition Metal-ligand Multiple Bond Complexes written by Paul Dermot Lyne and published by . This book was released on 1993 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Implementing New Ligand Platforms for Metal-ligand Multiple Bond and Dinitrogen Chemistry by : Keith Searles
Download or read book Implementing New Ligand Platforms for Metal-ligand Multiple Bond and Dinitrogen Chemistry written by Keith Searles and published by . This book was released on 2015 with total page 254 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Three-fold Symmetry for New Iron Metal-ligand Multiple Bonds and Multinuclear Complexes by : Juan A. Valdez-Moreira
Download or read book Three-fold Symmetry for New Iron Metal-ligand Multiple Bonds and Multinuclear Complexes written by Juan A. Valdez-Moreira and published by . This book was released on 2021 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Late transition metal complexes featuring terminal, multiple bonds with oxo, nitride, and imido ligands have been invoked as key intermediates in biorelevant small molecule transformations. Isolating these reactive intermediates is critical to understanding the mechanisms of such important transformations. The electronic stability imparted by a low-coordinate three-fold symmetric geometry allows these species to be isolated. Here, a strongly donating tris(carbene)borate ligand with large steric protection allows isolation and characterization of a previously unknown four-coordinate iron(III) terminal oxo complex, PhB(AdIm)3Fe=O. The extraordinarily short Fe-O bond distance in PhB(AdIm)3Fe=O indicates multiple bond character. EPR and Mossbauer spectroscopy reveal a low spin (S = 1/2) configuration. The iron oxo moiety readily reacts with a variety of C-H bonds, to yield the structurally characterized iron(II) hydroxide species, PhB(AdIm)3FeOH. The iron oxo complex is also a catalyst for phosphine oxidation. Moreover, the bulky tris(carbene)borate backbone stabilizes unique, mononuclear iron (III) terminal sulfide and disulfide complexes, allowing for their structural determination by single crystal X-ray diffraction. In contrast to the oxo analog, spectroscopic studies (EPR, Mossbauer) support a high spin (S = 5/2) iron terminal sulfide, while the iron disulfide adopts an intermediate spin configuration (S = 3/2). Three-fold symmetry can also confer rare electronic states, such as high spin iron cyanide complexes, which serve as building blocks in the construction of novel magnetic clusters. A rare high spin (S = 2) iron(II) monocyanide, (PhB(tBuIm)3FeCN), can be synthesized by the controlled reaction of an iron(II) fluoride complex with equimolar Me3SiCN. The resulting four-coordinate complex reacts with three-coordinate Mo(N(Ar)tBu)3 to form a cyanide bridged bimetallic species with a strongly activated cyanide ligand. Magnetic characterization of this Fe-Mo bimetallic species reveals strong antiferromagnetic coupling through cyanide. Moreover, two equivalents of PhB(tBuIm)3FeCN react with one equivalent of the two-coordinate iron(I) synthon, (PhB(tBuIm)2Fe(n6-tol)), to form a triiron cyanide cluster, [Ph2B(tBuIm)2Fe[NCFe(PhB(tBuIm)3)]2]. The triiron cyanide cluster has an S = 11/2 ground state with strong ferromagnetic coupling through cyanide. Low symmetry and strong donors also allowed the isolation of a strong ferromagnetic dihydride bridged diiron complex ([Ph2B(tBuIm)2FeH]2) with unusual symmetry at each iron center. Overall, these results show the advantages of low coordinate complexes.
Book Synopsis Metal-carbon Multiple Bond Formation at Molybdenum and Tungsten Centers Supported by Chelating Amido Ligands by : Frank Victor Cochran
Download or read book Metal-carbon Multiple Bond Formation at Molybdenum and Tungsten Centers Supported by Chelating Amido Ligands written by Frank Victor Cochran and published by . This book was released on 2002 with total page 284 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Studies of Low Valent Main Group and Transition Metal Complexes Supported by Nitrogen-based Ligands by : Audra Faye Lugo
Download or read book Studies of Low Valent Main Group and Transition Metal Complexes Supported by Nitrogen-based Ligands written by Audra Faye Lugo and published by . This book was released on 2009 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Monometallic and Bimetallic Complexes with Sulfonamido-Based Tripodal Ligands by : Nathanael Lau
Download or read book Monometallic and Bimetallic Complexes with Sulfonamido-Based Tripodal Ligands written by Nathanael Lau and published by . This book was released on 2017 with total page 145 pages. Available in PDF, EPUB and Kindle. Book excerpt: A central tenet of chemistry is the importance of the local environments that surround molecules. Rules for how such local environments control molecular properties have been developed and form the basis for coordination chemistry, an area of chemistry devoted to the study of molecules containing metal ions. Within this context, the volume of space surrounding metal ions is divided into two regions, referred to as the primary and secondary coordination spheres. The primary coordination sphere involves covalent interactions between atoms on ligands that are directly bound to the metal center. The secondary coordination sphere, which involves non-covalent interactions, is part of the volume of space around the metal center and often interacts with the ligands of the primary coordination sphere. Together, the coordination spheres define the physical properties and reactivity of a metal ion. The importance of modulating both is seen within the active sites of metalloproteins, in which the interplay between the two coordination spheres allow these proteins to catalyze difficult reactions under ambient conditions, with selectivities and efficiencies that are currently unattainable in synthetic systems.One approach towards understanding how the two coordination spheres affect function involves specially designed ligands that account for effects in both coordination spheres. The aim of this dissertation is to study synthetic metal complexes that incorporate these types of ligands, and explore their fundamental physical, structural, and chemical properties. The ligands used are based on the tripodal sulfonamido-based ligand N,N',N"-[2,2',2"-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido) ([MST]3--). This ligand contains a tris(2-aminoethyl)amine (tren) backbone that allows for the preparation of four- or five-coordinate metal complexes with local C3 symmetry to control the primary coordination sphere. The trigonal environment leads to high-spin metal complexes, and the presence of three anionic nitrogen donors helps to stabilize relatively high oxidation states. Secondary coordination sphere effects are modulated through the sulfonamido moieties. The [MST]3-- ligand can support monometallic metal complexes with terminal hydroxido, aqua, or ammine ligands, as the sulfonamido moieties can accept H-bonds from H-atom containing exogenous ligands. Additionally, the sulfonamido O-atoms can serve as a secondary metal binding site, allowing discrete bimetallic complexes to be prepared with [MST] 3--.In this dissertation, new monometallic and bimetallic complexes with sulfonamido-based tripodal ligands were prepared, with the goal of understanding how the choice of ligands influences the properties of metal complexes. The first study investigated the effect of ligand modification on the physical properties of a series of FeII--OH2 complexes supported by ligands related to [MST]3--. The aryl groups of the five new N,N',N"-[2,2',2"-nitrilotris(ethane-2,1-diyl)]-tris-({R-Ph}-sulfonamido)) ([RST]3--) ligands had para-substituents of varying electron-withdrawing and donating strengths. The physical properties of the subsequent Fe II--OH2 complexes were probed by various characterization methods, which revealed that the greatest impact of the ligand modification occurred in the metal complexes' electrochemical properties.Monometallic Ni complexes with [MST]3-- and a related urea-based ligand, [H3buea]3--, were then studied. The solid-state structures of these compounds showed that these ligands allowed for the preparation of NiII complexes with terminal aqua or hydroxido ligands in distorted trigonal bipyramidal geometries. Additionally, the oxidation chemistry of both NiII compounds was investigated, allowing for the preparation and characterization of uncommon NiII I complexes.Bimetallic complexes with [MST]3-- are prepared by treating a solution of a monometallic [MST]3-- complex, secondary metal salt, and secondary multidentate ligand with O2. The secondary ligand serves to "cap" the secondary metal center, resulting in discretely bimetallic units. A new series of bimetallic complexes with FeII(OH)FeIII, CoII(OH)Fe III, and NiII(OH)FeIII cores was prepared, using the bidentate capping ligand tetramethylethylenediamine (TMEDA). Previously, all other capping ligands used in this system had denticities of three and above. The bidentate capping ligand TMEDA allows the previously outer-sphere trifluoromethansulfonate (OTf--) counter anion to become inner-sphere, occupying the sixth coordination site of the second metal center.
