Study of Rhodium and Silver Complexes with Thioether- and Sulfoxide-functionalized N-heterocycliccarbene Ligands PDF Download
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Author: 余祈瑩
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Author: 余祈瑩
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Author: Afzal Hussain
Publisher: Springer Nature
ISBN: 3031356314
Category : Science
Languages : en
Pages : 84
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This book describes the emergence and recent advances in the design and development of rhodium complexes as therapeutic agents. Different classes of anticancer rhodium complexes with particular emphasis on ligands containing nitrogen-oxygen donor atoms are presented. Anticancer rhodium complexes of N-heterocyclic carbenes are described, while half-sandwich, heterobimetallic, and multinuclear rhodium complexes are discussed. Therapeutic applications of rhodium complexes beyond cancer such as antibacterial agents or antiviral agents are also analyzed, among others. Their mechanism of action is overviewed in detail, and the authors thoroughly comment on the challenges and future outlooks of research in the development of rhodium metallodrugs. This title highlights the important research carried out in the development of therapeutic rhodium complexes and is of great interest to graduates and researchers working in the area of rhodium-based therapeutic drugs.
Author: Granny Kabelo Ramollo
Publisher:
ISBN:
Category : Carbenes (Methylene compounds)
Languages : en
Pages : 250
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In this study, novel rhodium(I) carbene complexes were synthesized and fully characterized via a carbene ligand transfer methodology from Group 6 Fischer carbene complex precursors and subsequent ligand modification. The classic Fischer route was followed towards the isolation of mono- and biscarbene complexes of the form [M(CO)5{C(OR)R'}] [M = Cr, W; R = Me, Et; R' = 2-furyl, 2-thienyl, ferrocenyl] (complexes 1 6, 9 and 10), and [M(CO)5?{C(OR)-R''-C(OR)}M(CO)5] [M = Cr; R = Me, Et; R'' = 2,2'-bithien-5,5'-diyl, 2,5-furadiyl, 1,1'-ferrocendiyl] (complexes 7, 8 and 11), respectively. Analogous aminocarbene complexes [M(CO)5{C(NH2)R'}] [M = Cr, W; R' = 2-thienyl, ferrocenyl) (complexes 12 and 13) were prepared by simple aminolyses of the alkoxycarbene complex precursors and all isolated products were characterized using NMR and FT-IR spectroscopic methods, the results of which were comparable with literature values. Transmetallation techniques were employed in an attempt to transfer the carbene ligands to a rhodium(I) metal center of the dimeric [Rh(cod)Cl]2 precursor to result in novel 2-furyl, 2-thienyl and ferrocenyl Fischer carbene complexes of rhodium(I). Only the ferrocenylcarbene complex 15 [Rh(cod)Cl{C(OEt)Fc) were found to be stable enough to isolate, as the heteroaryl (thienyl, furyl) substituted carbene ligands dissociated in solution, with resultant decomposition dimerization to form the corresponding alkene and starting [Rh(cod)Cl]2 complex, as indicated by NMR spectroscopy. The ferrocenylcarbene complex 15 was then employed as a precursor for the syntheses of all other rhodium(I) carbene complexes via cod ligand substitution and aminolysis reactions to isolate mono- and dicarbonylcarbene complexes 16 23, [Rh(LL)Cl{C(X)Fc}] [LL = cod, (CO)2, (CO, PPh3), (CO, PCy3), (CO, P(OPh3)), (CO, AsPh3); X = OEt,NHnPr], with variable ?-acceptor properties. Full characterization of the novel complexes were achieved by single crystal XRD and spectroscopic methods. From the FT-IR data collected, the donor ability of the electronic environment around the rhodium(I) center was found to correlate with the known electron-donor ability of the coligands in the order PCy3>PPh3,AsPh3>P(OPh)3. This trend was corroborated by cyclic voltammetric methods through which the electron-withdrawing effects of the coligands were studied, and it was confirmed that the cod ligand is the most electrondonating whilst the dicarbonyls were found to be the least donating in the series. In addition, the increased electron donation of the aminocarbene ligands compared to the ethoxycarbene ligands was found to significantly influence the redox potentials of the metal centre in the studied complexes. The isolated rhodium(I) Fischer carbene complexes 15 - 22 were screened as catalyst precursors for the hydroformylation of 1-octene. Good to excellent catalytic activities, with selectivity toward the formation of the linear nonanal, was observed. These results were found to be comparable to results reported for rhodium(I) N-heterocyclic carbene complexes. A mercury-drop test was done to exclude a heterogeneous catalytic mode of action. Finally, the stability of the catalyst precursor 15 (and 17) was probed by an NMR experiment carried out under hydroformylation conditions. The Rh-Ccarbene bond is retained, although the presumed catalytically active species, the rhodium carbene carbonyl hydride complex could not be identified.
Author: Roxy Joanne Lowry
Publisher:
ISBN:
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: Jeremy PRAETORIUS
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Author: Li-Xin Dai
Publisher: John Wiley & Sons
ISBN: 3527322809
Category : Science
Languages : en
Pages : 433
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This book meets the long-felt need for a reference on ferrocenes with the focus on catalysis. It provides a thorough overview of the synthesis and characterization of different types of chiral ferrocene ligands, their application to various catalytic asymmetric reactions, and versatile chiral materials as well as drug intermediates synthesized from them. Written by the "who's who" of ferrocene catalysis, this is a guide to the design of new ferrocene ligands and synthesis of chiral synthetic intermediates, and will thus be useful for organic, catalytic and synthetic chemists working in academia, industrial research or process development.
Author: J. A. McCleverty
Publisher: Newnes
ISBN: 0080913164
Category : Science
Languages : en
Pages : 11845
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Comprehensive Coordination Chemistry II (CCC II) is the sequel to what has become a classic in the field, Comprehensive Coordination Chemistry, published in 1987. CCC II builds on the first and surveys new developments authoritatively in over 200 newly comissioned chapters, with an emphasis on current trends in biology, materials science and other areas of contemporary scientific interest.
Author: Montserrat Diéguez
Publisher: John Wiley & Sons
ISBN: 3527804072
Category : Technology & Engineering
Languages : en
Pages : 431
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An important reference for researchers in the field of metal-enzyme hybrid catalysis Artificial Metalloenzymes and MetalloDNAzymes in Catalysis offers a comprehensive review of the most current strategies, developed over recent decades, for the design, synthesis, and optimization of these hybrid catalysts as well as material about their application. The contributors—noted experts in the field—present information on the preparation, characterization, and optimization of artificial metalloenzymes in a timely and authoritative manner. The authors present a thorough examination of this interesting new platform for catalysis that combines the excellent selective recognition/binding properties of enzymes with transition metal catalysts. The text includes information on the various applications of metal-enzyme hybrid catalysts for novel reactions, offers insights into the latest advances in the field, and contains an informative perspective on the future: Explores the development of artificial metalloenzymes, the modern and strongly evolving research field on the verge of industrial application Contains a comprehensive reference to the research area of metal-enzyme hybrid catalysis that has experienced tremendous growth in recent years Includes contributions from leading researchers in the field Shows how this new catalysis combines the selective recognition/binding properties of enzymes with transition metal catalysts Written for catalytic chemists, bioinorganic chemists, biochemists, and organic chemists, Artificial Metalloenzymes and MetalloDNAzymes in Catalysis offers a unique reference to the fundamentals, concepts, applications, and the most recent developments for more efficient and sustainable synthesis.
Author: Iwao Omae
Publisher: Springer Science & Business Media
ISBN: 4431546049
Category : Science
Languages : en
Pages : 214
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This book provides a review of cyclometalation reactions and organometallic intramolecular-coordination five-membered ring products, the most active type of reactions in synthetic organic reactions and their products. Included is the discovery of intramolecular-coordination bonds in cyclometalation reactions and the characteristics of those reactions, as well as the reasons that their five-membered ring compounds are very easily synthesized through such reactions. In addition, the applications of cyclometalation reactions and five-membered ring products, synthetic applications, catalysts, and other products are described. These topics are of special interest for industrial researchers.
Author: Xue Duan
Publisher: Springer
ISBN: 9783540104940
Category : Science
Languages : en
Pages : 204
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