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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: 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: Antonio Togni Publisher: John Wiley & Sons ISBN: 352761558X Category : Science Languages : en Pages : 560
Book Description
With applications ranging from asymmetric catalysis to magnetic materials, ferrocene is one of the most versatile building blocks in synthesis. This book captures the multidisciplinary nature of ferrocene research, including topics such as ferrocene-containing polymers, ferrocene-containing thermotropic liquid crystals, chiral ferrocene derivatives, and ferrocene-containing charge-transfer materials. In addition, the reader will find * valuable information for planning syntheses * over 70 tables, making relevant data available at a glance * carefully selected references, providing an easy access to the primary literature Up-to-date, and written by leading international experts in the field, among them R. Deschenaux, C. D. Hall, Y. Butsugan, and R. Herrmann, this book is a welcome source of in-depth information for graduate students and professionals in organic, organometallic, and polymer chemistry, as well as in materials science.
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: B.I. Kharisov Publisher: Elsevier ISBN: 0128110627 Category : Science Languages : en Pages : 470
Book Description
Direct Synthesis of Metal Complexes provides in-depth coverage of the direct synthesis of coordination and organometallic compounds. The work is primarily organized by methods, but also covers highly relevant complexes, such as metal-polymer coordination compounds. This updated reference discusses recent developments in cryosynthesis, electrosynthesis, and tribosynthesis (popular as it doesn’t require organic solvents), with special attention paid to ‘greener’ methodologies and approaches. Additionally, the book describes physical methods of zero-valent metal interaction with organic matter, including sputtering, ultrasonic treatment and synthesis in ionic liquids. The book presents completely new content as a follow-up to the 1999 Elsevier Science publication Direct Synthesis of Coordination and Organometallic Compounds that was edited by Dr. Garnovskii and Dr. Kharisov. Covers current methods and techniques of metal interactions with organic media leading to metal chelates, adducts, di- and polymetallic complexes, metal-containing macrocycles, supported coordination compounds (i.e., metal complexes on carbon nanotubes), and more Describes reactivities of distinct forms of elemental metals (powders, sheets, nanoparticles (including a host of less-common metal nanostructures) with organic phase (liquid, solid and gaseous) and water Includes experimental procedures, with examples of direct synthesis, at the end of each chapter
Author: Li-Xin Dai Publisher: John Wiley & Sons ISBN: 3527322809 Category : Science Languages : en Pages : 433
Book Description
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: Jonathan Lee Brosmer Publisher: ISBN: Category : Languages : en Pages : 155
Book Description
Reliable transformation of low-cost rare-earth metal oxides to organometallic rare-earth metal complexes is a prerequisite for the advancement of non-aqueous rare-earth metal chemistry. We have recently developed an in situ method to prepare rare-earth alkyl and halide precursors supported by a diamidoferrocene NNfc, 1,1'-fc(NSiMe2Bu)2, as an ancillary ligand. We extended the scope of this method to other lanthanide ions including those that are redox active, such as cerium, praseodymium, samarium, terbium, thulium, and ytterbium. Specifically, samarium trisbenzyl could be generated in situ and then converted to the corresponding samarium benzyl or iodide complexes in good yield. However, it was found that ytterbium trisbenzyl could not be formed cleanly and the consequent conversion to ytterbium iodide complex was low yielding. By adapting an alternative route, the desired ytterbium chloride precursor could be obtained in good yield and purity. The synthesis and characterization of two yttrium alkyl complexes supported by a bisphosphinimine ferrocene ligand, NPfc (1,1 -di(2,4-di-tert-butyl-6-diphenylphosphiniminophenoxy)ferrocene), were accomplished. Although (NPfc)Y(CH2Ph) and (NPfc)Y(CH2SiMe3) could be structurally characterized, these compounds are thermally sensitive and decompose at ambient temperature within hours. Their characterization was accomplished by NMR spectroscopy, electrochemical measurements, and elemental analysis. Reactivity studies were also carried out; however, the lack of prolonged thermal stability at ambient temperature of these molecules led to decomposition before a clean transformation to reaction products could be observed. The synthesis and characterization of Ln-C4Ph4-K, [(NNTBS)Ln( 2-C4Ph4)][K(THF)x] (Ln = Sc, Y, Lu), rare-earth metal complexes supported by a ferrocene diamide ligand, NNTBS (NNTBS = fc(NSitBuMe2)2, fc = 1,1 -ferrocenediyl), were accomplished. The preparation of the half-sandwich compounds, Ln-naph-K, [(NNTBS)Ln( -C10H8)][K(THF)2] (Ln = Sc, Y, Lu, La), was necessary in order to obtain high yields of rare-earth metallacyclopentadienes. Unlike Y and Lu, La did not show the same reactivity toward PhCCPh. The characterization of the new metal complexes was accomplished by NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction.
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: Jun Gao Publisher: ISBN: Category : Languages : en Pages : 70
Book Description
Ferrocene chelating ligands provide good stability of the resulting metal complexes and redox-switchable control in chemical processes catalyzed by those complexes. In comparison to traditional di-substituted ferrocene tetradentate ligands, mono-substituted tridentate ferrocene ligands may form metal complexes with a more open coordination sphere around the metal center that may allow an increased preference for substrate coordination. In addition, a mono-substituted ferrocene ligand allows the investigation of the through bond influence of the ferrocenyl group on catalytic metal centers by increasing the metal-iron distance. In this thesis, the design, synthesis, and characterization by 1H NMR spectroscopy of a novel mono-substituted ferrocene ligand are described. To explore its ability to support metal complexes with high activity and redox-switchable in polymerization reactions, yttrium alkoxide and aluminum alkyl complexes were also synthesized and characterized by 1H NMR spectroscopy.
Author: Wilson D. Bailey Publisher: ISBN: Category : Alkenes Languages : en Pages : 181
Book Description
Late transition-metal pincer complexes of primarily palladium(II) and platinum(II) have been investigated for their application as catalysts in partial oxidation reactions. The epoxidation of higher olefins using molecular oxygen as the oxidant has been targeted, and the individual reaction steps needed to accomplish this overall transformation are described herein, including: (1) hydrogenolysis of a metal hydroxide (M-OH) species to yield a metal hydride (M-H), (2) insertion of O2 into the M-H bond to form a metal hydroperoxide (M-OOH), and (3) O-atom transfer from the M-OOH to epoxides, yielding a M-OH and completing the catalytic cycle. Previous results from our group on these individual transformations using (tBuPCP)Pd and (tBuPCO)Pd fragments are also reviewed. The requirements for O2 insertion into PdII and PtII hydrides are discussed. An array of cationic, neutral, and anionic Pd-H and Pt-H complexes supported by a tBuPNP backbone were synthesized and evaluated for O2 insertion (tBuPNP = 2,6-bis-(di-tbutylphosphinomethyl)pyridine). Metal-ligand cooperation was observed in the activation of H2 to form neutral hydride complexes. The effect of ligand protonation/deprotonation on the trans influence experienced by the hydride ligand was investigated. No reaction with O2 was observed with the cationic hydrides, while the neutral and anionic forms reacted with O2 at the tBuPNP backbone. The synthesis and characterization of mono- and dinuclear Pd-OH complexes supported by a PCNR pincer ligand (PCNR = (1-(3-((di-tert-butylphosphino)methyl)phenyl)-1H-5-R-pyrazole), R = H, Me) is presented. When R = H, ligand pyrazole "rollover" C-H activation was observed, forming a mixed ligand (PCNH)Pd(μ-OH)Pd(PCC) dinuclear structure. This "rollover" was investigated using DFT computations. The mono- and dinuclear hydroxide species were evaluated for hydrogenolysis. The dinuclear compounds {[(PCNR)Pd]2(μ-OH)}[OTf] reacted under an H2 atmosphere to yield the corresponding dinuclear hydrides {[(PCNR)Pd]2(μ-H)}[OTf]. A mechanistic study on the hydrogenolysis of the μ-bridged hydroxide {[(PCNMe)Pd]2(μ-OH)}[OTf] revealed first order kinetics in both [Pd] and [H2]. Terminal hydrides were not detected, and reduction of the mononuclear hydroxide complexes (PCNR)Pd-OH to Pd0 was observed under H2. The reduction was proposed to proceed through displacement of the pyrazole arm, and was examined by DFT computations. Lastly, a new strategy to promote O-atom transfer from M-OOH to epoxides, the final step in the targeted catalytic cycle, is proposed. Preliminary studies on NNNPyz, NNNEt, and NNMe ligated PdII and PtII are discussed (NNNPyz = 2,6-bis(5-tbutyl-1H-pyrazol-3-yl)pyridine; NNNEt = 2-(5-tbutyl-1H-pyrazol-3-yl)-6-(diethylaminomethyl)pyridine; NNMe = 2-(5-tBu-1H-pyrazol-3-yl)-6-methylpyridine). The NNNPyz ligand, containing two acidic sites in proximity to the fourth site in the square plane, was found to protonate M-O2 complexes, chelate to the metal center and oxidize phosphine substrates. Similar reactivity was observed with NNNEt and NNMe, however hemilability of these ligands resulted in undesired coordination modes.
Author: Yi Shen
Author: Yi Shen
Author: Antonio Togni
Author: Brian Raymond Lydon
Author: B.I. Kharisov
Author: Li-Xin Dai
Author: Jonathan Lee Brosmer
Author: Mark Abubekerov
Author: Jun Gao
Author: Christopher R. Yeisley
Author: Wilson D. Bailey