Synthesis And Reactivity Of Transition Metal Complexes Containing Ligands With Hydrogen Bonding Moieties
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Synthesis And Reactivity Of Transition Metal Complexes Containing Ligands With Hydrogen Bonding Moieties
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Author : Hayley Ann Burkill
language : en
Publisher:
Release Date : 2006
Synthesis And Reactivity Of Transition Metal Complexes Containing Ligands With Hydrogen Bonding Moieties written by Hayley Ann Burkill and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2006 with categories.
Synthesis And Reactivity Of Transition Metal Complexes Containing Hydrogen Bonding Moieties
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Author :
language : en
Publisher:
Release Date : 2006
Synthesis And Reactivity Of Transition Metal Complexes Containing Hydrogen Bonding Moieties written by and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2006 with categories.
Synthesis Structure And Reactivity Of Transition Metal Complexes Containing P O And N Donor Ligands
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Author :
language : en
Publisher:
Release Date : 2001
Synthesis Structure And Reactivity Of Transition Metal Complexes Containing P O And N Donor Ligands written by and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2001 with categories.
Investigating The Effects Of Non Covalent Interactions In Metal Complexes With Versatile Ligand Scaffolds
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Author : Nathaniel Solomon Sickerman
language : en
Publisher:
Release Date : 2014
Investigating The Effects Of Non Covalent Interactions In Metal Complexes With Versatile Ligand Scaffolds written by Nathaniel Solomon Sickerman and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2014 with categories.
In Nature, transition metal-containing enzymes have evolved to catalyze a wide variety of chemical reactions with astounding efficiencies and selectivities through precise control of their primary and secondary coordination environments. Taking inspiration from the active sites of metalloenzymes, synthetic bioinorganic chemists have endeavored to construct metal complexes that model the structures and functions of these enzymes. Controlling the primary coordination spheres of metal ions to model active sites is accomplished through the construction of metal-binding organic ligand frameworks, but the resulting metal complexes often lack the activities observed in their biological counterparts. Non-covalent secondary coordination sphere effects that are present within metalloenzyme active sites are integral to the proper function of these proteins and have been more challenging to emulate within synthetic systems. Manipulation of the secondary coordination environment surrounding synthetic metal complexes can be accomplished by using rigid ligand scaffolds containing groups that promote non-covalent interactions proximal to the metal center. The Borovik group has developed a number of tetradentate ligands that can bind metal ions and establish a pocket where external ligands can bind to the metal center. The ligands contain moieties that interact with the metal-bound exogenous ligands through non-covalent effects, particularly hydrogen bonds (H-bonds). This dissertation chronicles the advances made with two tripodal ligand platforms that promote intramolecular H-bonding networks within the resulting complexes. The first ligand studied, TAO, tautomerizes upon metal ion binding to provide a neutral N4 primary coordination environment to the metal center. This tautomerization event places H-bond donating groups proximal to external ligands that can bind to the metal center, producing intramolecular H-bonding networks. TAO complexes are sufficiently flexible to accommodate ligands of varying sizes, shapes, and charges. The versatility of the TAO framework is exemplified through a series of metal complexes which have been characterized in both the solution and solid state. Ab initio theoretical calculations performed on many of these complexes provide insight into the electronic effects of the H-bonding interactions. The ligand [MST]3 binds metal ions in a similar manner to TAO, but possesses sulfonamido groups that render the complex cavity capable of both accepting H-bonds and binding secondary metal ions. The bifunctionality of [MST]3 has been explored through the synthesis of heterobimetallic complexes wherein the metal ions are bridged by a hydroxido group. The work on [MST]3 in this dissertation focuses on diamagnetic main group analogs of these complexes whose structures could be elucidated in both the solution and solid states. The structurally characterized complexes were found to retain their supramolecular structures in solution. The relevance of some of these complexes to the oxygen evolving complex within Photosystem II is also discussed. Additionally, M-NH3 (M = Fe11, Fe111, Ga111) complexes are presented that contain intramolecular H-bonding networks and which remain assembled in both solution and the solid state. A putative Fe111-NH2 species and its reactivity is discussed, and the synthesis and structure of a Ga111-N2H4 complex is documented. A new N4 donor ligand platform, [POAT]3− is presented in the final portion of this dissertation. In complexes with this ligand, phosphine oxide groups are positioned within the secondary coordination sphere of the metal center to act as H-bond acceptors and to bind additional metal ions. While these features are akin to those in the [MST]3 system, preliminary studies indicate that the primary coordination sphere is much more reducing; as such, complexes with [POAT]3− are anticipated to stabilize metal complexes in higher oxidation states.
Organometallic Chemistry
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Author : Ian J S Fairlamb
language : en
Publisher: Royal Society of Chemistry
Release Date : 2014-06-30
Organometallic Chemistry written by Ian J S Fairlamb and has been published by Royal Society of Chemistry this book supported file pdf, txt, epub, kindle and other format this book has been release on 2014-06-30 with Science categories.
A series of critical reviews and perspectives focussing on specific aspects of organometallic chemistry interfacing with other fields of study are provided. For this volume, the critical reviews cover topics such as the activation of "inert" carbon-hydrogen bonds, ligand design and organometallic radical species. For example, Charlie O'Hara discusses how mixed-metal compounds may perform the highly selective activation of C-H bonds and, in particular, how synergic relationships between various metals are crucial to this approach. The chemistry of a remarkable series of air-stable chiral primary phosphine ligands is discussed in some depth by Rachel Hiney, Arne Ficks, Helge M3ller-Bunz, Declan Gilheany and Lee Higham. This article focuses on the preparation of these ligands and also how they may be applied in various catalytic applications. Bas De Bruin reports on how ligand radical reactivity can be employed in synthetic organometallic chemistry and catalysis to achieve selectivity in radical-type transformations. As well as highlighting ligand-centered radical transformations in open-shell transition metals, an overview of the catalytic mechanism of Co(II)-catalysed olefin cyclopropanation is given, showing that enzyme-like cooperative metal-ligand-radical reactivity is no longer limited to real enzymes. Valuable and informative comprehensive reviews in the field of organometallic chemistry are also covered in this volume. For example, organolithium and organocuprate chemistry are reviewed by Joanna Haywood and Andrew Wheatley; aspects in Group 2 (Be-Ba) and Group 12 (Zn-Hg) compounds by Robert Less, Rebecca Melen and Dominic Wright; metal clusters by Mark Humphrey and Marie Cifuentes; and recent developments in the chemistry of the elements of Group 14 - focusing on low-coordination number compounds by Richard Layfield. This volume therefore covers many synthetic and applied aspects of modern organometallic chemistry which ought to be of interest to inorganic, organic and applied catalysis fields.
Synthesis Characterization And Reactivity Of Transition Metal Complexes Containing Multi Donor Ligands
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Author : John C. Linehan
language : en
Publisher:
Release Date : 1986
Synthesis Characterization And Reactivity Of Transition Metal Complexes Containing Multi Donor Ligands written by John C. Linehan and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1986 with categories.
Synthesis And Reactivity Of Late Transition Metal Complexes Featuring A Bis 8 Quinolyl Methylsilyl Ligand
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Author : Preeyanuch Sangtrirutnugul
language : en
Publisher:
Release Date : 2007
Synthesis And Reactivity Of Late Transition Metal Complexes Featuring A Bis 8 Quinolyl Methylsilyl Ligand written by Preeyanuch Sangtrirutnugul and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2007 with categories.
Synthesis And Reactivity Of Transition Metal Complexes Using Ligands Capable Of Variable Electron Donation
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Author : Gregory A. Marinelli
language : en
Publisher:
Release Date : 1992
Synthesis And Reactivity Of Transition Metal Complexes Using Ligands Capable Of Variable Electron Donation written by Gregory A. Marinelli and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1992 with categories.
Synthesis And Reactions Of Dinuclear Transition Metal Complexes Containing Bridging Ligands Relevant To Heterogeneous Catalysis
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Author : Eric Niels Jacobsen
language : en
Publisher:
Release Date : 1986
Synthesis And Reactions Of Dinuclear Transition Metal Complexes Containing Bridging Ligands Relevant To Heterogeneous Catalysis written by Eric Niels Jacobsen and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1986 with categories.
Macromolecules Containing Metal And Metal Like Elements Volume 6
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Author : Alaa S. Abd-El-Aziz
language : en
Publisher: John Wiley & Sons
Release Date : 2005-10-27
Macromolecules Containing Metal And Metal Like Elements Volume 6 written by Alaa S. Abd-El-Aziz and has been published by John Wiley & Sons this book supported file pdf, txt, epub, kindle and other format this book has been release on 2005-10-27 with Technology & Engineering categories.
This series provides a useful, applications-oriented forum for the next generation of macromolecules and materials. The sixth volume in this series provides useful descriptions of the transition metals and their applications, edited by high-quality team of macromolecular experts from around the world.
