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Author: Alan Martin Allgeier Publisher: ISBN: Category : Languages : en Pages :
Book Description
A new redox-active HE(II) sequestering ligand, ($\eta\sp5$-C$\rm\sb5H\sb4SCH\sb2CH\sb2SH)\sb2$Fe, 5, has been synthesized and characterized. Ligand 5 undergoes a reaction with Hg(ClO$\sb4)\sb2$, which has been detected by $\sp1$H NMR spectroscopy and cyclic voltammetry in DMSO.
Author: Alan Martin Allgeier Publisher: ISBN: Category : Languages : en Pages :
Book Description
A new redox-active HE(II) sequestering ligand, ($\eta\sp5$-C$\rm\sb5H\sb4SCH\sb2CH\sb2SH)\sb2$Fe, 5, has been synthesized and characterized. Ligand 5 undergoes a reaction with Hg(ClO$\sb4)\sb2$, which has been detected by $\sp1$H NMR spectroscopy and cyclic voltammetry in DMSO.
Author: Brian Raymond Lydon Publisher: ISBN: Category : Languages : en Pages : 67
Book Description
This thesis contains results from three different projects. The first project focused on the synthesis of monoanionic ferrocene-based N, P ligands. 1-(tert-butyldimethylsilyl)amino-1'-diphenylphosphinoferrocene (fc(TBSNH)(PPh2)) was successfully synthesized and characterized by 1H, 31P, 13C NMR spectroscopy, and elemental analysis. Unfortunately, coordination to group 3 metal complexes was unsuccessful. The second project focused on the synthesis of redox-active ferrocene-based ligands and their applications in selective intramolecular hydroamination. Redox-active ligands can be used as a reversible trigger to control catalytic reactivity. Preliminary results observed by 1H NMR spectroscopy suggest that [1,1'-ferrocenedi(thio(3,5-di-tert-butyl-2-phenoxide)]Zr dibenzyl ((thiolfan2)ZrBn2) shows selectivity between primary and secondary alkeneamines depending on the oxidation state of the iron center. The final project was a computational study using density functional theory (DFT) to understand recent experimental findings involving ferrocene-functionalized biodegradable polymers. Gibbs free energy for six cyclic carbonate monomers and three [delta]-valerolactone monomers was calculated. Computational results correlated strongly with experimental data in that [delta]-valerolactones, which could not be polymerized, had a higher Gibbs free energy than cyclic carbonates, which could be polymerized.
Author: Yi Shen Publisher: ISBN: Category : Languages : en Pages : 0
Book Description
Developing methodologies to synthesize high-value products efficiently from simple substrates with control over the reactivity and selectivity is highly favored by the chemical industry. Employing assisted tandem catalysis, where serial reactions can be carried out in one pot, to achieve streamlined complex syntheses significantly reduces the number of steps and waste. Harnessing spatial and temporal control in catalysis enables approaches toward one-pot transformations and allows the integration of several catalytic processes. Ferrocene-based ligand-supported metal complexes represent a promising class of catalysts that can incorporate redox control over catalytic processes. We have developed a redox-controlled selective hydroamination reaction catalyzed by (thiolfan*)Zr(NEt2)2 (thiolfan*= 1, 1'-bis (2,4-di-tert-butyl-6-thiophenoxy)ferrocene). In situ switching of the catalyst's state during the reaction enables selectivity toward different substrates (Chapter 2).Incorporating the greenhouse gas CO2 into N-carboxyanhydrides (NCAs) followed by subsequent NCA utilization illustrates the possibility of integrating two synthetic steps in one vessel to afford a valuable material with possible CO2 recycling. To demonstrate the immense potential of integrating multi-step transformations in one pot, we developed a set of sustainable conditions for NCA synthesis (Chapter 3). Moreover, several metal catalysts supported by ferrocene-based ligands were found to catalyze NCA polymerization in the presence of a co-catalyst. To establish an integrated system composed of two incompatible processes, we aimed to compartmentalize the active reagents for each step. The structure of the ferrocene-based pro-ligand was modified for surface anchoring. Our efforts toward immobilizing ferrocene-supported metal catalysts onto conductive surfaces pave the way of achieving spatiotemporal control over the processes of NCA synthesis and polymerization (Chapter 4). In addition to the redox-switchable characteristic, ferrocene-based compounds provide a unique platform to support lanthanides and engender distinctive optical properties to them. We synthesized and characterized a series of ytterbium complexes displaying an ultra-narrow absorption in the ultraviolet-visible (UV-Vis) region. The extraordinarily narrow linewidth observed for (thiolfan)YbCl(THF) (thiolfan = 1,1'-bis(2,4-di-tert-butyl-6-thiomethylenephenoxy)ferrocene) allows us to investigate its applications toward magnetic field and liquid cell quantum sensing (Chapter 5).
Author: Petr Stepnicka Publisher: John Wiley & Sons ISBN: 9780470985656 Category : Science Languages : en Pages : 670
Book Description
Ferrocene—the prototypical metallocene—is a fascinating molecule. Even though it was first discovered over fifty years ago, research into ferrocene-containing compounds continues apace, largely stimulated by their successful applications in catalysis, materials science and bioorganometallic chemistry. Ferrocene derivatives are now recognised as useful starting materials for the preparation of new organometallic complexes and functional materials, efficient catalyst components, as well as redox-active modifiers to biomolecules. Ferrocenes: Ligands, Materials and Biomolecules provides the reader with a background overview and describes recent advances in the development and application of ferrocene compounds, including: synthesis and catalytic utilisation of chiral and non-chiral ferrocene ligands ferrocene-based sensors electrooptical materials ferrocene polymers liquid-crystalline materials crystal engineering with ferrocene compounds the bioorganometallic chemistry of ferrocene Ferrocenes: Ligands, Materials and Biomolecules is an essential guide for anyone working in the fields of organometallic synthesis and catalysis, materials science and bioorganometallic chemistry.
Author: Tate Reuter Publisher: ISBN: Category : Languages : en Pages : 66
Book Description
Ferrocene-chelating heteroscorpionate compounds based on [fc(PPh2)(BH[(3-R-5-R'-1-H)2pz]2)] (fc = 1,1'-ferrocenediyl, pz = pyrazole) are studied and characterized for their role in the synthesis of block copolymers. The ferrocene scaffold is part of a heteroscorpionate ligand that supports late transition metals. A zinc complex, [fc(PPh2)(BH[(3,5-Me-1H)2pz]2)]Zn( -OCH2Ph), was synthesized previously and shown to exist in a dimeric state. Herein, the substituents on the pyrazole fragments of the scorpionate are replaced with bulkier groups to force the formation of a monomeric compound in order to arrive at a redox switchable catalyst.
Author: Mark Abubekerov Publisher: ISBN: Category : Languages : en Pages : 327
Book Description
The synthesis of new polymers is motivated by the limitations of current materials. Recently, interest in copolymers containing blocks that display different or complementary properties has been increasing since these materials have potential for further performance enhancements. Inspired by recent developments in olefin polymerization catalysts, and based on the interest of the Diaconescu group in the reactivity of complexes supported by ferrocene-based chelating ligands, we developed a new ferrocene-chelating heteroscorpionate supporting ligand and investigated its applications in combination with late transition metals to redox-switchable catalysis for the production of multiblock copolymers. Additionally, we began investigations into the influence of the iron-secondary metal interactions on redox-switchable catalysis in complexes supported by symmetrically substituted, neutral ferrocene-based ligands.
Author: Marine Desage-El Murr Publisher: John Wiley & Sons ISBN: 3527348506 Category : Science Languages : en Pages : 373
Book Description
Redox-Active Ligands Authoritative resource showcasing a new family of ligands that can lead to better catalysts and promising applications in organic synthesis Redox-Active Ligands gives a comprehensive overview of the unique features of redox-active ligands, describing their structure and synthesis, the characterization of their coordination complexes, and important applications in homogeneous catalysis. The work reflects the diversity of the subject by including ongoing research spanning coordination chemistry, organometallic chemistry, bioinspired catalysis, proton and electron transfer, and the ability of such ligands to interact with early and late transition metals, lanthanides, and actinides. The book is divided into three parts, devoted to introduction and concepts, applications, and case studies. After the introduction on key concepts related to the field, and the different types of ligands and complexes in which ligand-centered redox activity is commonly observed, mechanistic and computational studies are described. The second part focuses on catalytic applications of redox-active complexes, including examples from radical transformations, coordination chemistry and organic synthesis. Finally, case studies of redox-active guanidine ligands, and of lanthanides and actinides are presented. Other specific sample topics covered include: An overview of the electronic features of redox-active ligands, covering their historical perspective and biological background The versatility and mode of action of redox-active ligands, which sets them apart from more classic and tunable ligands such as phosphines or N-heterocyclic carbenes Preparation and catalytic applications of complexes of stable N-aryl radicals Metal complexes with redox-active ligands in H+/e- transfer transformations By providing up-to-date information on important concepts and applications, Redox-Active Ligands is an essential reading for researchers working in organometallic and coordination chemistry, catalysis, organic synthesis, and (bio)inorganic chemistry, as well as newcomers to the field.
Author: Kenneth D. Karlin Publisher: John Wiley & Sons ISBN: 0470167068 Category : Science Languages : en Pages : 616
Book Description
Straight from the frontier of scientific investigation . . . Nowhere is creative scientific talent busier than in the world of inorganic chemistry. And the respected Progress in Inorganic Chemistry series has long served as an exciting showcase for new research in this area. With contributions from internationally renowned chemists, this latest volume reports the most recent advances in the field, providing a fascinating window on the emerging state of the science. "This series is distinguished not only by its scope and breadth, but also by the depth and quality of the reviews." —Journal of the American Chemical Society "[This series] has won a deservedly honored place on the bookshelf of the chemist attempting to keep afloat in the torrent of original papers on inorganic chemistry." —Chemistry in Britain CONTENTS OF VOLUME 48: Synthesis, Structure, and Properties of Organic-Inorganic Perovskites and Related Materials (David B. Mitzi, IBM T. J. Watson Research Center, Yorktown Heights, New York). Transition Metals in Polymeric 1 - Conjugated Organic Frameworks (Richard P. Kingsborough and Timothy M. Swager, Massachusetts Institute of Technology, Cambridge, Massachusetts). The Transition Metal Coordination Chemistry of Hemilabile Ligands (Caroline S. Slone, Dana A. Weinberger, and Chad A. Mirkin, Northwestern University, Evanston, Illinois). Organometallic Fluorides of the Main Group Metals Containing the C-M-F Fragment (Balaji R. Jagirdar, Eamonn F. Murphy, and Herbert W. Roesky, Universität Göttingen, Germany). Coordination Complex Impregnated Molecular Sieves-Synthesis, Characterization, Reactivity, and Catalysis (Partha P. Paul, Southwest Research Institute, San Antonio, Texas). Advances in Metal Boryl and Metal-Mediated B-X Activation Chemistry (Milton R. Smith III, Michigan State University, East Lansing, Michigan).
Author: Philippe Kalck Publisher: Springer Nature ISBN: 3031322509 Category : Science Languages : en Pages : 241
Book Description
This book presents recent advances in dinuclear complexes in which the metal-metal cooperative effect operates for obtaining substrate activation and high performance catalysts. Catalysis continues to be a fast expanding area to design efficient tools in synthesis and in industrial chemistry. It allows performing syntheses with short reaction times, atom economy, reduced consumption of energy and loss of reagents, and low level of wastes. Dinuclear complexes are known to be more efficient than the mononuclear analogues for the reaction rates and the selectivities. This book analyses the latest research, focusing on the key concepts, in building and using these dinuclear complexes. The book is aimed at researchers, graduate students and chemists at all levels in academia and industry.
Author: Alan Martin Allgeier
Author: Alan Martin Allgeier
Author: Brian Raymond Lydon
Author: Yi Shen
Author: Petr Stepnicka
Author: Tate Reuter
Author: Mark Abubekerov
Author: Marine Desage-El Murr
Author: Niki Sachsinger
Author: Kenneth D. Karlin
Author: Philippe Kalck