Computationally Guided Rational Ligand Design of Novel Iridium (I) Complexes for Elevated Substrate Applicability in Hydrogen Isotope Exchange Processes PDF Download
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Author: Gary J. Knox
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Languages : en
Pages :
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Author: Gary J. Knox
Publisher:
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Languages : en
Pages :
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Author: Renan Zorzatto
Publisher:
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Category :
Languages : en
Pages : 0
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The development of catalytic systems for the functionalisation of carbon-hydrogen bonds has been an intensive area of research for the last 5 decades. In this context, transition metal complexes play a crucial role in reaction discovery, mechanistic evaluation and synthetic applications. In the Kerr group, this technology has been explored in the context of hydrogen isotope exchange, resulting in the development of highly active iridium(I) complexes bearing phosphines and NHC ligands. Despite their broad functional group compatibility, existing methods for isotope exchange are ineffective in the labelling of sterically encumbered directing groups. Hence, in the first chapter we investigate the synthesis of three new iridium(I) complexes bearing chelating phosphine-functionalised NHC ligands, and their application in the isotope exchange of sterically hindered carbamates. Our initial studies revealed high catalytic efficiency and tolerance for steric encumbrance, prompting us to perform a combined theoretical and experimental investigation of the reaction mechanism.Therefore, by conducting DFT calculations and kinetic experiments, we were able to identify a rich dynamic behaviour in solution and ultimately propose a reaction mechanism. Additionally, our interest in the activation of carbon-hydrogen bonds resulted in the exploration of a theoretical model for the prediction of enthalpies of activation, resulting in the identification of relevant electronic and steric descriptors.From the knowledge gathered in our initial studies, the second chapter describes the application of our novel iridium catalysts in the functionalisation of carbon-hydrogen bonds in the context of hydroarylation of olefins. Thus, we identified carboxylic acids as suitable directing groups for this transformation and employed Design of Experiments to optimise the reaction conditions. Synthetic studies were focused on the preparation of 14 substrates, enabling quick assessment of the capabilities and limitations of this reaction. These investigations resulted in a synthetic method suitable for the synthesis of bi- and tricycles featuring tertiary and quaternary benzylic stereocentres in a racemic fashion.Finally, we investigated the mechanism of this process by DFT calculations, which led us to identify a plausible reaction pathway which should guide future kinetic evaluations.
Author: Philippa Kate Owens
Publisher:
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Languages : en
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Author: Luis A. Oro
Publisher: John Wiley & Sons
ISBN: 3527623086
Category : Science
Languages : en
Pages : 424
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Ranging from hydrogenation to hydroamination, cycloadditions and nanoparticles, this first handbook to comprehensively cover the topic of iridium in synthesis discusses the important advances in iridium-catalyzed reactions, namely the use of iridium complexes in enantioselective catalysis. A must for organic, complex and catalytic chemists, as well as those working with/on organometallics.
Author: Stephanie Irvine
Publisher:
ISBN:
Category :
Languages : en
Pages : 634
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Author: Luis A. Oro
Publisher: Springer Nature
ISBN: 3030690830
Category : Science
Languages : en
Pages : 461
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This new volume “Iridium Catalysts for Organic Reactions” in the series “Topics in Organometallic Chemistry” intends to update several representative well-known reactions and to introduce other less known or new reactions in particular covering sustainability aspects. Iridium complexes are efficient in many catalytic homogeneous transformations providing high efficiency in both results, activity and selectivity. The interest of the book lies in the presentation of the advances, new perspectives and application in a variety of representative iridium-catalysed reaction. All chapters in the volume are contributed by relevant international experts in the field. The book is aimed at researchers, graduate students and synthetic chemists at all levels in academia and industry.
Author: Wayne M. Rees
Publisher:
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Category :
Languages : en
Pages : 578
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Author:
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Languages : en
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Nuclear power is an attractive alternative to hydrocarbon-based energy production at a time when moving away from carbon-producing processes is widely accepted as a significant developmental need. Hence, the radioactive actinide power sources for this industry are necessarily becoming more widespread, which is accompanied by the increased risk of exposure to both biological and environmental systems. This, in turn, requires the development of technology designed to remove such radioactive threats efficiently and selectively from contaminated material, whether that be contained nuclear waste streams or the human body. Raymond and coworkers (University of California, Berkeley) have for decades investigated the interaction of biologically-inspired, hard Lewis-base ligands with high-valent, early-actinide cations. It has been established that such ligands bind strongly to the hard Lewis-acidic early actinides, and many poly-bidentate ligands have been developed and shown to be effective chelators of actinide contaminants in vivo. Work reported herein explores the effect of ligand geometry on the linear U(IV) dioxo dication (uranyl, UO2{sup 2+}). The goal is to utilize rational ligand design to develop ligands that exhibit shape selectivity towards linear dioxo cations and provides thermodynamically favorable binding interactions. The uranyl complexes with a series of tetradentate 3-hydroxy-pyridin-2-one (3,2-HOPO) ligands were studied in both the crystalline state as well as in solution. Despite significant geometric differences, the uranyl affinities of these ligands vary only slightly but are better than DTPA, the only FDA-approved chelation therapy for actinide contamination. The terepthalamide (TAM) moiety was combined into tris-beidentate ligands with 1,2- and 3,2-HOPO moieties were combined into hexadentate ligands whose structural preferences and solution thermodynamics were measured with the uranyl cation. In addition to achieving coordinative saturation, these ligands exhibited increased uranyl affinity compared to bis-Me-3,2-HOPO ligands. This result is due in part to their increased denticity, but is primarily the result of the presence of the TAM moiety. In an effort to explore the relatively unexplored coordination chemistry of Pu(IV) with bidentate moieties, a series of Pu(IV) complexes were also crystallized using bidentate hydroxypyridinone and hydroxypyrone ligands. The geometries of these complexes are compared to that of the analogous Ce(IV) complexes. While in some cases these showed the expected structural similarities, some ligand systems led to significant coordination changes. A series of crystal structure analyses with Ce(IV) indicated that these differences are most likely the result of crystallization condition differences and solvent inclusion effects.
Author: Roxy Joanne Lowry
Publisher:
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Category :
Languages : en
Pages :
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ABSTRACT: Eighty-five percent of all industrial chemical processes occur catalytically. The world's expanding appetite for mass production of exotic chemicals necessitates the design and application of enhanced catalysts. To optimize catalytic materials, the detailed relationships between catalyst architecture and reactivity must be determined. Although for many ligand families these relationships are well understood, novel catalysts require in depth empirical investigation to determine these connections. The design of a novel di-N-heterocyclic carbene family of ligands in reported herein. These C2 symmetric ligands are based on the rigid 9,10-dihydro-9,10-ethanoanthracene backbone and designed for utilization in chiral catalysis. Thorough investigation into the relationships between the ligand's structure and the architecture of the resulting rhodium and iridium catalysts directed the design of three generations of our novel ligand family. The first generation, trans-1,1'-[9,10-dihydro-9,10-ethanoanthracene-11,12- diyldimethanediyl]bis(benzylimidazole) bis(triflouromethansulfonate) [DEAM-BI](OTf)2 (2-1), is too flexible to enforce a rigid chiral pocket about a metal center under catalytic conditions. The constrained second generation ligands, trans-1,1'-(9,10-dihydro-9,10-ethanoanthracene.
Author: Nathan Knight
Publisher:
ISBN:
Category :
Languages : en
Pages : 0
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