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Synthesis Characterization And Applications Of Complexes Involving Redox Active Ligands
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Book Synopsis Synthesis, Characterization and Applications of Complexes Involving Redox-active Ligands by : Romain Kunert
Download or read book Synthesis, Characterization and Applications of Complexes Involving Redox-active Ligands written by Romain Kunert and published by . This book was released on 2022 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: We developed a new type of redox-active ligand, involving two N-heterocyclic carbenes and two phenolate units. The strong electron donating properties of the NHC moieties were utilized to stabilize complexes in high oxidation states while the phenolate groups were used as redox-active units. Group 10 metal complexes were developed. Their oxidation chemistry showed the formation of phenoxyl radicals, reaching up to two-electron oxidized, bis(phenoxyl) complexes. We also report the first Ni(III) complex with NHC donors. The ligand was also used to develop metal complexes with nitride ligands. The nitridomanganese complex proved to be unstable and degraded in successive intramolecular nitride-NHC reductive couplings. The degradation afforded a peculiar organic salt with three fused rings forming a central triazone pattern. Conversely, the chromium nitride complex could be isolated and thoroughly characterized. The one-electron oxidized product was generated reversibly at low temperature but readily evolved at room temperature. In a parallel work, we also developed new types of sterically hindered salen ligands to form distorted copper salen complexes as molecular models of galactose oxidase. The copper salen catalysts showed to be effective for the aerobic oxidation of non-activated alcohol substrates.
Book Synopsis The Synthesis, Characterization, and Oxidation-state Dependent Reactivity of Rh(I) Complexes Formed from Novel Redox-active Ligands by : Caroline Cassano Slone
Download or read book The Synthesis, Characterization, and Oxidation-state Dependent Reactivity of Rh(I) Complexes Formed from Novel Redox-active Ligands written by Caroline Cassano Slone and published by . This book was released on 1997 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Redox-Active Ligands by : Marine Desage-El Murr
Download or read book Redox-Active Ligands written by Marine Desage-El Murr and published by John Wiley & Sons. This book was released on 2024-02-05 with total page 373 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Synthesis, Characterization, and Reactivity Studies of Iron Complexes Supported by the Redox-active [ONO] Ligand by : Janice Lin Wong
Download or read book Synthesis, Characterization, and Reactivity Studies of Iron Complexes Supported by the Redox-active [ONO] Ligand written by Janice Lin Wong and published by . This book was released on 2014 with total page 123 pages. Available in PDF, EPUB and Kindle. Book excerpt: The work reported herein primarily focuses on the development of new platforms for multi-electron reactivity using iron complexes supported by a redox-active pincer-type ligand. This dissertation details the synthesis, characterization, and reactivity of iron complexes coordinated to the redox-active [ONO] ([ONO]H3 = bis(3,5-di-[tert]-butyl-2-phenol)amine) ligand. Chapter 1 provides a general background on ligand-centered and metal-centered redox reactivity. Specifically, the characteristics of redox-active ligands and their ability to promote multi-electron reactivity at redox-inert metal centers is presented. In addition, iron-catalyzed organic transformations in which the metal center undergoes redox changes is also discussed. Finally, ligand-enabled redox reactions mediated by iron complexes containing redox-active ligands is described. Chapter 2 reports on the complexation of bis(3,5-di-[tert]-butyl-2-phenoxy)amine, [ONHO], and the redox-active [ONO] ligands by iron centers to afford a new family of iron complexes. Characterizations of each compound through a battery of analytical techniques reveal the oxidation states of the metal center and ligand. Furthermore, the electronic properties of each complex were investigated in order to evaluate their potential to facilitate multi-electron reactivity. Chapter 3 details the reactivity of the [ONO]Fe platform. Metathesis reactions are conducted with [ONO [superscript q] Fe [superscript III] X2 (X = Cl, N[SiMe3]2 complexes, demonstrating the capability of the fully-oxidized [ONO [superscript q]−1 to act as a two-electron acceptor to generate the fully reduced [ONO [superscript cat]3− that is coordinated to an iron(III) center. Similarly, oxidation of [ONO[superscript cat] Fe [superscript III] (py)3 (py = pyridine) using dihalogens result in two-electron oxidations of the tridentate ligand while the metal oxidation state remains the same. These redox reactions showcase the ability of the [ONO] ligand platform to undergo reversible two-electron oxidation state changes, allowing multi-electron reactivity to occur at the iron center. The synthesis and characterization of two novel bimetallic complexes of the form [ONO]M'[ONO]2 M (M' = Fe, Zn; M = Fe) are presented in Chapter 4. The rich redox profiles of both complexes suggest that they can potentially impart unique cooperative bimetallic reactivity. The synthetic techniques developed to prepare these complexes lay the foundation for a general method to access new bimetallic combinations that could be promising for multi-electron reactivity. Finally, Chapter 5 discusses the synthesis, characterization, and electronic comparisons between two homoleptic tris-iminosemiquinonate chromium(III) compounds. While one is coordinated to three N,N'-bis(3,5-dimethylphenyl)acenapthenediimino-semiquinonate, (dmp-ADI [superscript sq])1−, ligands, the other contains three N,N'-bis(3,5-dimethylphenyl)phenanthrenediimino-semiquinonate, (dmp-PDIsq)1− ligands. The differences in the electronic properties between each complex likely stems from variation in the diimine ligand backbones. However, further investigation is required to completely understand the complicated behaviors of such complexes, both of which apparently exhibit intramolecular anti-ferromagnetic properties.
Book Synopsis The Age of Noninnocence by : Seth N. Brown
Download or read book The Age of Noninnocence written by Seth N. Brown and published by Wiley. This book was released on 2017-01-24 with total page 368 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book presents a comprehensive introduction to the unique and fundamental features of redox-active ligands, the preparation and characterization of their coordination complexes, and finally the importance of this class of molecules to biology, catalysis and materials. The book aims to provide a broadly accessible introduction to the particular features and opportunities unique to redox-active ligands. It begins with an introduction to the intellectual challenges posed by redox-active ligands and descriptions of the types of ligands and complexes in which ligand-centered redox activity are commonly observed. Following this, the book is divided into two sections as follows: The first section focuses on electronic structure and bonding, which has historically dominated this field and continues to be actively researched. The spectroscopic and other physical measurements that have been used to elucidate the electronic structure of these compounds are described. The interplay between synthesis, bonding models, and physical measurements has often been critical in shaping our understanding of these compounds. This interplay is illustrated by a number of case studies. The second section focuses on the use of redox-active complexes in stoichiometric and catalytic reactions. The scope of known reactions is presented, including examples from bioinorganic chemistry (both enzymes and model compounds). Where possible, the significance of the redox-active ligand is discussed, with an eye both to summarizing existing knowledge and pointing out possibilities for future research. This book explains the underpinnings of physical and theoretical techniques of redox-active ligands, providing up to date information on definitions, scope and applications for research scientists and graduate students working in organic and inorganic chemistry, organometallics and coordination chemistry.
Book Synopsis Vanadium Catalysis by : Manas Sutradhar
Download or read book Vanadium Catalysis written by Manas Sutradhar and published by Royal Society of Chemistry. This book was released on 2020-11-05 with total page 526 pages. Available in PDF, EPUB and Kindle. Book excerpt: Vanadium is one of the more abundant elements in the Earth’s crust and exhibits a wide range of oxidation states in its compounds making it potentially a more sustainable and more economical choice as a catalyst than the noble metals. A wide variety of reactions have been found to be catalysed by homogeneous, supported and heterogeneous vanadium complexes and the number of applications is growing fast. Bringing together the research on the catalytic uses of this element into one essential resource, including theoretical perspectives on proposed mechanisms for vanadium catalysis and an overview of its relevance in biological processes, this book is a useful reference for industrial and academic chemists alike.
Book Synopsis Design and Synthesis of a Series of Redox Active Tetrazine and Triazine Based Transition Metal Complexes by : Yixin Zhang
Download or read book Design and Synthesis of a Series of Redox Active Tetrazine and Triazine Based Transition Metal Complexes written by Yixin Zhang and published by . This book was released on 2018 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The use of two different chelating redox active ligands, 2,6-bis(6-methyl-1,2,4,5-3-yl) pyridine (BTZP) and 2,6-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-pyridine (BTP) in heterometallic first row and second row transition metal chemistry has yielded two new families of redox active metal complexes. These complexes were found to exhibit interesting electrochemical and magnetic properties. In this thesis, Chapter 1 lays the foundation for the research presented within. This section covers the fundamentals of the ligand design, ligand synthesis and related coordination chemistry literature review. Chapters 2 and 3 report the results of the current thesis. In Chapter 2, the synthesis and characterization of a family of discrete molecules and supramolecular arrangements, employing the ligand BTZP, is presented. All of the complexes presented in Chapter 2 are successfully synthesized and characterized with electrochemical and magnetic studies. According to the electrochemical data, it is found that the classic "terpy-like" complexes with [Co(BTZP) 2]2+ formula fosters more stability in the redox process. In Chapter 3, a family of transition metal complexes with [M(BTP) 2]2+ (M=Fe or Co) inorganic cores were obtained through the employment of the ligand BTP with various anions. In addition, dimeric molecules with [CoX4(BTP)2] formula were also obtained by solvothermal synthesis. The complexes were also electrochemically characterized, with all the complexes capable of being reduced, while only [CoII(BTP)2] (ClO4)2 showed reversible redox process. Similar with BTZP, the series of BTP based complexes are also characterized through magnetic measurement. Only cobalt-based BTP complexes are paramagnetic, with [CoII(BTP)2]2+ being spin crossover active when BF4- and ClO4- are present. However, the presence of NCS- and halides lead to either antiferromagnetic interactions and ferromagnetic interactions dominating at different temperature regimes.
Book Synopsis Synthesis, Characterization and Coordination Chemistry of Pincer Ligands Based on (benzannulated) Pyridines by : Jason Braun
Download or read book Synthesis, Characterization and Coordination Chemistry of Pincer Ligands Based on (benzannulated) Pyridines written by Jason Braun and published by . This book was released on 2020 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: The idea of 'non-innocent' ligands is that the site of chemical or redox activity on a coordination complex may not be solely limited to the central atom. Ligands may participate either by themselves or in cooperation with a central atom to facilitate electron-transfer and/or chemical reactivity in a more active fashion than in a typical coordination complex. Each of the projects explored in this thesis include the common theme of pyridine-based pincer-type ligands, their coordination to late transition metals and main group elements, and how the reactivity and properties of these complexes involves both the ligand and the ligated element. To do so, a comprehensive investigation of the electronic structure of complexes supported by pincer-type, 'NNN' ligands is also described. Diiminepyridine ligands tend to actively participate in the chemistry of their complexes. Taking advantage of these non-innocent ligands has allowed for the stabilization of unusual oxidation states of transition metal complexes as well as the facilitation of chemical transformations with metals unable to do so using spectator ligands. Pseudo-octahedral iron complexes of these ligands exhibit multiple reversible reductions and are shown to be viable candidates as anolytes for redox flow battery applications. In synthesizing these, a synthetic scheme to prepare these ligands with electron withdrawing groups on the flanking aryl groups was developed, opening up the chemical space for these new ligands in the already well-established field of diiminepyridine ligand chemistry. In addition, bulky analogues engender stabilization of phosphorus complexes in the +1 and +3 oxidations states, not seen before with traditional diiminepyridine ligands. The synthetic route to diarlyamido ligands comprised of flanking quinoline (2,3-benzopyridine) and phenanthridine (3,4-benzoquinoline) donors has also been developed and the coordination of these monoanionic ligands to a variety of late transition metals and main group elements was explored. Several aspects of this ligand can be deemed non-innocent and will be highlighted throughout the course of this thesis. We see an unusual electronic environment of pseudo-octahedral iron complexes of these ligands that exhibit record length charge-transfer excited states and panchromatic absorption. Exchanging the central metal can bring about mixed-valent species upon oxidation evidenced by strong absorption in the near infrared region of the electromagnetic spectrum that significantly depends on metal-ligand orbital overlap.
Book Synopsis Molecular Clusters of the Main Group Elements by : Matthias Driess
Download or read book Molecular Clusters of the Main Group Elements written by Matthias Driess and published by John Wiley & Sons. This book was released on 2008-11-21 with total page 460 pages. Available in PDF, EPUB and Kindle. Book excerpt: With more than 20 contributions from leading research groups, this book provides essential information for chemists and materials scientists working with molecular clusters. It treats both homonuclear and heteronuclear clusters, including: the theory and concepts in main-group cluster chemistry, * novel boranes and heteroboranes, * silicon/germanium/tin clusters, * alkali metal suboxides, * clusters in alloys with mercury, * chalkogen clusters * and numerous other compound classes. The whole is illustrated by examples of the great potential for technical applications such as electron storage, cancer therapy and in optoelectronic devices. Its systematic coverage of all relevant main group elements makes this the prime reference source in the field.
Book Synopsis Synthesis, Characterization, and Reactivity of Transition Metal Complexes Supported by Heteropolydentate Ligation by : Adam Ruddy
Download or read book Synthesis, Characterization, and Reactivity of Transition Metal Complexes Supported by Heteropolydentate Ligation written by Adam Ruddy and published by . This book was released on 2014 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Design, Synthesis and Characterization of New Coordination Compounds with Biologically Active Ligands by : Suneel Lanka
Download or read book Design, Synthesis and Characterization of New Coordination Compounds with Biologically Active Ligands written by Suneel Lanka and published by . This book was released on 2023 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis The Group 13 Metals Aluminium, Gallium, Indium and Thallium by : Simon Aldridge
Download or read book The Group 13 Metals Aluminium, Gallium, Indium and Thallium written by Simon Aldridge and published by John Wiley & Sons. This book was released on 2011-02-10 with total page 990 pages. Available in PDF, EPUB and Kindle. Book excerpt: The last two decades have seen a renaissance in interest in the chemistry of the main group elements. In particular research on the metals of group 13 (aluminium, gallium, indium and thallium) has led to the synthesis and isolation of some very novel and unusual molecules, with implications for organometallic synthesis, new materials development, and with biological, medical and, environmental relevance. The Group 13 Metals Aluminium, Gallium, Indium and Thallium aims to cover new facts, developments and applications in the context of more general patterns of physical and chemical behaviour. Particular attention is paid to the main growth areas, including the chemistry of lower formal oxidation states, cluster chemistry, the investigation of solid oxides and hydroxides, advances in the formation of III-V and related compounds, the biological significance of Group 13 metal complexes, and the growing importance of the metals and their compounds in the mediation of organic reactions. Chapters cover: general features of the group 13 elements group 13 metals in the +3 oxidation state: simple inorganic compounds formal oxidation state +3: organometallic chemistry formal oxidation state +2: metal-metal bonded vs. mononuclear derivatives group 13 metals in the +1 oxidation state mixed or intermediate valence group 13 metal compounds aluminium and gallium clusters: metalloid clusters and their relation to the bulk phases, to naked clusters, and to nanoscaled materials simple and mixed metal oxides and hydroxides: solids with extended structures of different dimensionalities and porosities coordination and solution chemistry of the metals: biological, medical and, environmental relevance III-V and related semiconductor materials group 13 metal-mediated organic reactions The Group 13 Metals Aluminium, Gallium, Indium and Thallium provides a detailed, wide-ranging, and up-to-date review of the chemistry of this important group of metals. It will find a place on the bookshelves of practitioners, researchers and students working in inorganic, organometallic, and materials chemistry.
Book Synopsis Synthesis, Electronic Delocalization and Applications of Octahedral Bis(imino)pyridine Group 13 Metal Complexes by : Amela Arnold (Drljevic)
Download or read book Synthesis, Electronic Delocalization and Applications of Octahedral Bis(imino)pyridine Group 13 Metal Complexes written by Amela Arnold (Drljevic) and published by . This book was released on 2020 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation discusses the synthesis, characterization and electronic delocalization of bis(imino)pyridine (I2P) complexes of the Group 13 metals Al, Ga and In. This work aims to understand the electronic communication between redox-active ligands bridged by a main group metal and apply this research for storing multiple electrons in nonaqueous redox-flow battery applications. The introduction to this dissertation details the background on redox-active ligands, mixed valency and redox flow batteries. A future outlook on this field is presented. The work presented here has contributed to our understanding of delocalization of charge in organic molecules, and how delocalization is affected by increasing charge, appending electron-donating or withdrawing functional groups or varying the metal bridge. Evidence for a symmetric nonaqueous redox flow battery is presented. In Chapter 2, ligand-based mixed valency is introduced. Water stable organic mixed valence (MV) compounds were prepared by reaction of reduced bis(imino)pyridine ligands (I2P) with the trichloride salts of Al, Ga, and In. Coordination of two tridentate ligands to each ion affords octahedral complexes that are accessible with five ligand charge states: [(I2P0)(I2P−)M]2+, [(I2P−)2M]+, (I2P−)(I2P2−)M, [(I2P2−)2M]−, [(I2P2−)(I2P3−)M]2−, and for M = Al only, [(I2P3−)2M]3−. In solid-state structures the anionic members of the redox series are stabilized by intercalation of Na+ cations within the ligands. The MV members of the redox series, (I2P−)(I2P2−)M and [(I2P2−)(I2P3−)M]2−, show characteristic intervalence transitions, in the near-infrared region between 6800 - 7400 and 7800 - 9000 cm-1, respectively. Cyclic voltammetry (CV), NIR spectroscopic, and X-ray structural studies support the assignment of Class II for compounds [(I2P2−)(I2P3−)M]2− and Class III for M = Al and Ga in (I2P−)(I2P2−)M. All compounds containing a singly reduced I2P− ligand exhibit a sharp, low energy transition in the region 5100 - 5600 cm−1 that corresponds to a [pi]* - [pi]* transition. CV studies demonstrate that the electron transfer events in each of the redox series, Al, Ga, and In span 2.2, 1.4 and 1.2 V, respectively. In Chapter 3, ligand-based mixed valent (MV) complexes of Al(III) incorporating electron donating (ED) and electron withdrawing (EW) substituents on bis(imino)pyridine ligands (I2P) are presented. The MV states (I2P−)(I2P2−)Al and [(I2P2−)(I2P3−)Al]2− prepared containing EW groups are both assigned as Class II/III. The MV states prepared with incorporation of ED functional groups are Class III and Class II/III in the (I2P−)(I2P2−)Al and [(I2P2−)(I2P3−)Al]2− charge states, respectively. The assignments of the delocalized electronic structures were made using cyclic voltammetry (CV), and near infra-red (NIR) spectroscopy. The MV ligand charge states (I2P−)(I2P2−)Al and [(I2P2−)(I2P3−)Al]2− show intervalence charge transfer (IVCT) transitions at 6850-7740 and 7410-9780 cm−1, respectively. Alkali metal cations in solution had no effect on the IVCT bands of [(I2P2−)(I2P3−)Al]2− complexes containing ED -PhNMe2 substituents or EW -PhF5 substituents on the I2P ligands. Localization of charge in [(I2P2−)(I2P3−)Al]2− was observed when -PhOMe substituents are included on the I2P ligands, so that those complexes are Class II/III with K+ and Class III with K:(18-crown-6)+. In Chapter 4, the application of these redox-active octahedral Al(III) complexes as analytes for symmetric nonaqueous redox flow batteries is presented. Redox flow batteries (RFBs) operate by storing electrons on soluble molecular anolytes and catholytes, however large increases in the energy density of RFBs could be achieved if multiple electrons could be stored in each molecular analyte. Others have suggested and employed various transition element - redox active ligands combinations to realize multi-electron storage in anolytes, and a challenge with those efforts has been the analyte's stability over extended charging and discharging of multi-electron cycles. We reported an organoaluminum analyte in which four electrons can be stored on organic ligands, and for which charging and discharging cycles performed in a symmetric nonaqueous RFB configuration remain stable for over 100 cycles at 70% state of charge and 97% Coulombic efficiency. Stability is promoted by the kinetic inertness of the anolyte to trace water in solvents and by the redox stability of the Al(III) ion to the applied current. Proof-of principle experiments performed with an asymmetric NRFB configuration further demonstrate that up to four electrons can be stored in the cell with no degradation of the analyte over multiple cycles that show 96% Coulombic efficiency.
Book Synopsis Synthesis, Reactivity and Computational Studies of Redoxactive Indium Thiolate Complexes by : Padmapriya Srinivasan
Download or read book Synthesis, Reactivity and Computational Studies of Redoxactive Indium Thiolate Complexes written by Padmapriya Srinivasan and published by . This book was released on 2022 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Green Chemistry initiatives have recently been at the forefront of both industrial and academic communities in order to address fundamental scientific challenges of protecting human health and the environment. The Twelve Principles of Green Chemistry, of which catalysis is a primary tenet and the main motivation for this project, has led the path to reduce waste production in the chemical industry. The principle of catalysis states that catalytic reactions necessarily produce less waste than stoichiometric reactions. Traditionally, precious and toxic heavy transition metals such as platinum and palladium have been used as metal centres in catalysts because of their stability, favourable redox properties, and ease of characterization. These concerns prompted this research in finding more environmentally friendly alternatives as metal centres in catalysis, such as main group complexes. Indium is a heavy main group metal that is environmentally benign. It is most stable in the +3 oxidation state and, notably, does not possess other readily accessible oxidation states. To make indium complexes redox-active, so-called "non-innocent" redox-active ligands are being explored. The current work seeks to synthesize a series of redox-active indium catalysts with varied steric bulk about the indium centre and different redox-active ligands. The goals of this study are to first synthesize and structurally characterize organometallic indium compounds with the redox-active ligand 2-amninobenzenethiol, and then test the reactivity of indium complexes with dithiolate ligands using mild oxidizing agents. A third goal is to use DFT methods to rationalize the synthesized complexes in terms of structure, reactivity, bonding motifs, and in interpreting the experimental spectroscopic data.
Book Synopsis Conducting Metallopolymers with Tridentate Ligands and Coordination Chemistry with Corresponding Model Compounds by : Şeyma Keskin
Download or read book Conducting Metallopolymers with Tridentate Ligands and Coordination Chemistry with Corresponding Model Compounds written by Şeyma Keskin and published by . This book was released on 2013 with total page 380 pages. Available in PDF, EPUB and Kindle. Book excerpt: Conducting polymers that contain metals are remarkable materials, because they have the properties of both organic backbones and metals. Depending on the position of the metal relative to the conjugated backbone, i.e. attached to or directly in the backbone, these two can couple resulting in advancement of the functionality and therefore potential applications of these types of materials. Complexes of tridentate ligands with donor atoms such as phosphorus, nitrogen, and sulfur also have a wide variety of applications. In addition, complexes of tridentate ligands have advantages of stability and control of electron density by variation of donor atoms. Therefore, conjugated polymers with tridentate ligand units will have promise for various applications and advantages in their designs. Complexes of PNP ligand with molybdenum and carbonyl ancillary ligands were synthesized and characterized. Isomerization and conversion reactions between them were investigated as well as the coordination modes. Many types of PNP ligands have been studied in the literature because the hemilabile property of the nitrogen atom promotes some catalytic reactions and gives different coordination geometries. Conducting polymers can be used as redox-active ligands and they can be used to control electron density on the metal attached to them. Synthesis and characterization of a novel polymerizable ligand 3,5-bis-EDOT-N,N-bis[2-diphenylphosphinoethyl]aniline was achieved. Related molybdenum complexes with ancillary ligands as carbonyls were also synthesized and characterized. Monomer complexes and the free ligand were electropolymerized and studied. Tris(bipyridine)ruthenium(II) chloride and analogous complexes have been studied extensively in the literature due to their luminescent and photochemical properties, and excited state lifetimes. Conducting polymers with similar ruthenium groups have been investigated for various applications. Synthesis of four ruthenium complexes with the polymerizable ligand 2,6-Bis[4-[2-(3,4-diethylenedioxy)thiophene]pyrazol-1-yl]pyridine and four different bidentate ligands were reproduced; electropolymerizations of the complexes were achieved; electrochemical, UV-Vis and luminescence studies were performed and discussed. Various complexes of copper, silver, platinum, and palladium with nitrogen and phosphorus donors have been reported for their luminescence behavior as well as their interesting structures. Model complexes of these metals with N,N-bis[2-(diphenylphosphino)ethyl]phenyl-amine (a PNP ligand) have been synthesized and characterized. Absorption and luminescence behaviors as well as the coordination modes were investigated.
Book Synopsis Synthesis, Characterization, and Catalytic and Biological Activities of a Mixed-ligand Cobalt(ii) Bipyridyl/diphenylazodioxide Complex by : Kylin Alice Emhoff
Download or read book Synthesis, Characterization, and Catalytic and Biological Activities of a Mixed-ligand Cobalt(ii) Bipyridyl/diphenylazodioxide Complex written by Kylin Alice Emhoff and published by . This book was released on 2021 with total page 160 pages. Available in PDF, EPUB and Kindle. Book excerpt: Transition metal complexes have immense importance in the pharmaceutical industry. These types of complexes can be useful catalysts in the synthesis of medicinal compounds and can act as anticancer drugs. In these pharmaceutical applications, 1st-row transition metal-containing complexes offer certain advantages compared to their 2nd and 3rd-row transition metal counterparts. Our motivation was to investigate pharmaceutical applications of transition metal complexes containing both a 1st-row transition metal and unusual ligands to expand the knowledge of a class of complexes that could potentially be beneficial in the pharmaceutical industry. A class of rare ligands that piqued our interest was that of the diaryl azodioxides, cis-Ar(O)NN(O)Ar, which belong to the wider class of organic derivatives of nitric oxide (NO). Our synthesis and pharmaceutical applications of the azodioxide complex salt [Co(bpy){Ph(O)NN(O)Ph}2](PF6)2 have been able to significantly expand the knowledge of azodioxide complexes by displaying an unusual trigonal prismatic coordination geometry for cobalt(II) with only bidentate ligands, showing evidence of ligand-based redox activity, acting as an active catalyst in allylic amination/C0́2C double-bond transposition reactions, and selectively inducing apoptosis in SK-HEP-1 human liver adenocarcinoma cells. Importantly, catalytic and biological studies of [Co(bpy){Ph(O)NN(O)Ph}2](PF6)2 are ongoing, and focused on its potential for use in the pharmaceutical industry as a drug or catalyst for drug synthesis. Future work will involve comparing the catalytic and biological activities of [Co(bpy){Ph(O)NN(O)Ph}2](PF6)2 with other azodioxide complexes prepared by our group to identify structure-activity relationships and inform the design of more efficient catalysts and anti-cancer, pro-apoptotic agents.
Book Synopsis Design of Redox-active Ligands by : Nico Matteo Bonanno
Download or read book Design of Redox-active Ligands written by Nico Matteo Bonanno and published by . This book was released on 2021 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis describes the design, synthesis, properties, and coordination chemistry of redoxactive ligands. This thesis also explores new ways of expanding our ligand systems, in order to improve their binding capacities. We accomplished this by utilizing familiar redox-active moieties and structures to those published previously in our group, but with enhanced topological capacities and predictable structural outcomes. Chapter 1 begins with a general outline of the fundamental principles that govern organic radicals including; their reactivity, their properties and applications, and how these can be applied to the design of ligands for polynuclear assembly. Chapter 2 starts with a brief overview of arylazo ligands and the synthesis of a new hydrazone substituted phenalenol ligand (2.1). In the following section (2.2) we use this ligand to produce homoleptic ligand mixed-valence complexes featuring trivalent cobalt and iron metals. The chapter is concluded (2.3) with the synthesis of a new ditopic aryl-azo ligand and its cobalt coordination chemistry involving a neutral tetra-radical/tetra-nuclear molecular grid featuring valence tautomerism. Chapter 3 begins with the design and synthesis of a new ditopic diamino phenol ligand, which was found to oxidize to a neutral stable phenoxyl radical (3.1-3.2). The solution properties, which include reversible pi-dimerization of this stable radical are also described (3.3), and later the substitution chemistry of this new ligand is explored (3.4). In chapter 4, we describe the coordination chemistry of this new ditopic aminophenol ligand, which includes assembly into several coordination clusters involving copper (4.2), iron (4.3), nickel (4.4), and zinc (4.5). These coordination clusters feature the ligand in a variety of oxidation states; including rare examples of dianion "aminyl" radical clusters. In chapter 5, we begin with a description of a new synthetic derivative which can be used for the construction of larger tetratopic or asymmetric diamino phenol ligands. In 5.2 we describe the synthesis of a tetratopic aminophenol ligand along with its reactivity and aerial oxidation to a tri-phenoxyl radical. In 5.3, we conclude the thesis with the use of an asymmetric diamino phenol ligand and it's Cu(II/III) coordination chemistry, which displayed unique reactivity with molecular oxygen.
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