Ferrocene-Chelating Heteroscorpionate Ligands Support Zinc Complexes as Redox Switchable Catalysts PDF Download

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Ferrocene-Chelating Heteroscorpionate Ligands Support Zinc Complexes as Redox Switchable Catalysts

Ferrocene-Chelating Heteroscorpionate Ligands Support Zinc Complexes as Redox Switchable Catalysts PDF 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.

Ferrocene-Chelating Heteroscorpionate Ligands Support Zinc Complexes as Redox Switchable Catalysts

Ferrocene-Chelating Heteroscorpionate Ligands Support Zinc Complexes as Redox Switchable Catalysts PDF 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.

Symmetrically and Non-symmetrically Substituted 1,1'-ferrocenes as Supporting Ligands for Divalent Metals in Catalysis

Symmetrically and Non-symmetrically Substituted 1,1'-ferrocenes as Supporting Ligands for Divalent Metals in Catalysis PDF 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.

Synthesis of Metal Complexes Supported by Ferrocene-based Ligands for Tandem Catalysis and Applications Toward Liquid Cell Quantum Sensing

Synthesis of Metal Complexes Supported by Ferrocene-based Ligands for Tandem Catalysis and Applications Toward Liquid Cell Quantum Sensing PDF 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).

Ferrocenes

Ferrocenes PDF 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.

Synthesis of Yttrium and Aluminum Complexes Supported by a Mono-Substituted Ferrocene Ligand

Synthesis of Yttrium and Aluminum Complexes Supported by a Mono-Substituted Ferrocene Ligand PDF 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.

Synthesis of Ferrocene-based Ligands and Their Applications in Redox-switchable Catalysis for Selective Hydroamination Reactions

Synthesis of Ferrocene-based Ligands and Their Applications in Redox-switchable Catalysis for Selective Hydroamination Reactions PDF 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.

Ferrocene-based Redox-switchable Ligands

Ferrocene-based Redox-switchable Ligands PDF 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.

Polymer Molecular Weights

Polymer Molecular Weights PDF Author: Philip E. Slade
Publisher:
ISBN:
Category : Science
Languages : en
Pages : 360

Book Description


Activation of Small Molecules

Activation of Small Molecules PDF Author: William B. Tolman
Publisher: John Wiley & Sons
ISBN: 3527609377
Category : Science
Languages : en
Pages : 382

Book Description
The first to combine both the bioinorganic and the organometallic view, this handbook provides all the necessary knowledge in one convenient volume. Alongside a look at CO2 and N2 reduction, the authors discuss O2, NO and N2O binding and reduction, activation of H2 and the oxidation catalysis of O2. Edited by the highly renowned William Tolman, who has won several awards for his research in the field.

Handbook of Chalcogen Chemistry

Handbook of Chalcogen Chemistry PDF Author: Francesco Devillanova
Publisher: Royal Society of Chemistry
ISBN: 1849737460
Category : Science
Languages : en
Pages : 499

Book Description
The Handbook of Chalcogen Chemistry: New Perspectives in Sulfur, Selenium and Tellurium provides an overview of recent developments, particularly from the last decade, on the chemistry of the chalcogen group elements (S, Se and Te). While up to a few decades ago, chalcogen chemistry was mainly centred on sulphur, in recent years the research based on Se and Te has increased dramatically, and has created huge scope for the use of compounds based on this type of chemistry. The Handbook is organised into two parts, the first of which deals systematically with the chemistry of chalcogens in relation to other group elements in the periodic table. It also includes an overview of metal-chalcogenides and metal-polychalcogenides. The second part reflects the interdisciplinary nature of chalcogen chemistry and focuses on biological, materials and supramolecular aspects of the field. This Handbook gives a comprehensive overview on recent developments over the last decade and is ideal for researchers in the field.