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Articles 1 - 30 of 82
Full-Text Articles in Inorganic Chemistry
Luminescent Group 11 Metal (I) Chalcogen Clusters With A Conjugated Diphosphine Ligand, Kai Yu Jeffrey Li
Luminescent Group 11 Metal (I) Chalcogen Clusters With A Conjugated Diphosphine Ligand, Kai Yu Jeffrey Li
Electronic Thesis and Dissertation Repository
Polynuclear Au (I) complexes exhibit rich photochemical properties and have the potential to find applications as molecular sensors, switches, or energy storage devices. Although dinuclear Au (I) complexes with bridging diphosphines have been extensively examined, most of those reported do not contain rigid-diphosphine ligands.
This thesis examines how the rigid diphosphine, 4,6-bis(diphenylphosphino)dibenzofuran (DBFDP) can be incorporated for the controlled assembly of photoluminescent gold (I) metal – chalcogenolate (chalcogenolate = RS-, RSe-; R = organic moiety) and gold (I) chalcogenide (chalcogenide = S2-, Se2-) bimetallic complexes. In these studies, the chalcogen …
Exploring The Reactivity Of Metal-Ligand Cooperative Complexes With Dioxazolones, Terminal Alkynes, And 2-Ethynylbenzyl Alcohol, Megan A. Hoffer Miss
Exploring The Reactivity Of Metal-Ligand Cooperative Complexes With Dioxazolones, Terminal Alkynes, And 2-Ethynylbenzyl Alcohol, Megan A. Hoffer Miss
Electronic Thesis and Dissertation Repository
N-Acyl ketenimines were attempted to be synthesized catalytically by [Ru(Cp)(PPh2NPh2)(NCMe)]PF6 with phenylacetylene and 3-phenethynyl-1,2,4-dioxazol-5-one. Trapping agents were employed to identify the major product of the reaction, as many products were formed. [Ru(Cp)(PPh2NPh2)(NCMe)]PF6 reacts with 3-phenethynyl-1,2,4-dioxazol-5-one generating an isocyanate via the Curtius rearrangement, confirmed by a forced Curtius rearrangement with 3-phenethynyl-1,2,4-dioxazol-5-one and 1,2,4-triazole. Rates of vinylidene formation using [Ru(Cp)(PPh2NPh2)(NCMe)]PF6 and various terminal alkynes of different sterics and electronics were evaluated using a Hammett analysis for and simple rate comparisons. …
Investigating The Structure Of Metal-Organic Frameworks And The Behaviors Of Adsorbed Guest Molecules In Mofs Via Solid-State Nmr Spectroscopy, Yihao Shen
Electronic Thesis and Dissertation Repository
Metal-organic frameworks (MOFs) are a class of hybrid organic-inorganic microporous materials with lots of significant applications including gas capture and storage, gas separation, batteries, catalysis, ion exchange and drug delivery. MOFs based on s-block metals are important due to their many practical applications. These MOFs are also very interesting because the s-block MOFs often exhibit unpredictable behavior of coordination. In this thesis, the structures of six s-block metal (Li, Na, Cs, Mg, Ca, Sr) based MOFs involving V-shaped link, 4, 4′- sulfonyldibenzoate (SDB) are characterized by various techniques including, powder X-ray diffraction, TGA and solid-state NMR spectroscopy. 13C CPMAS …
Synthesis Of Ni(Ii) Complexes For Allylic C(Sp3)-H Bond Activation For Aerobic Oxidation Catalysis, Shagana Kukendran
Synthesis Of Ni(Ii) Complexes For Allylic C(Sp3)-H Bond Activation For Aerobic Oxidation Catalysis, Shagana Kukendran
Electronic Thesis and Dissertation Repository
Nickel is a widely abundant and inexpensive metal. Catalysts are substances that remain unconsumed and increase the rate of reactions by reducing the activation energy barrier, often by providing an alternative route. The main goal of this study is to prepare Ni(II) complexes that can promote a catalytic aerobic oxidation reaction by breaking allylic C-H bonds. Based on previous studies, allylnickel N-heterocyclic carbene complexes react with molecular oxygen to give useful carbonyl compounds with a Ni(II)-OH by-product, which undergoes dimerization. In order to achieve catalysis, dimerization of the Ni(II)-OH should be prevented and C-H activation has to be achieved to …
Synthesis And Surface Modification Of Azide Decorated Silver Nanoclusters, Alexander H. Stöckli
Synthesis And Surface Modification Of Azide Decorated Silver Nanoclusters, Alexander H. Stöckli
Electronic Thesis and Dissertation Repository
In nanocluster research, easy modification of the cluster surface while maintaining the cluster core remains a key challenge. Herein we report the synthesis, structure, and properties of four targeted Ag20 nanoclusters (NCs) with surface azide moieties, two of which have 8 azide moieties, [CO3@Ag20(StBu)10(m-N3-C6H4COO)8(DMF)4] and [CO3@Ag20(StBu)10(p-N3-C6H4COO)8(DMF)4], and two of which have 6 azide moieties, [CO3@Ag20(S …
The Synthesis, Lewis Acidity And Catalytic Activity Of Bis(Catecholato)Germanes, Andrew T. Henry
The Synthesis, Lewis Acidity And Catalytic Activity Of Bis(Catecholato)Germanes, Andrew T. Henry
Electronic Thesis and Dissertation Repository
Main group Lewis acids have been shown to be viable alternatives to state-of-theart transition metal catalysts. While extensive research into a variety of p-block Lewis acids have been reported, the field of germanium Lewis acid chemistry has been described as “almost non-existent”. A variety of bis(catecholato)germane derivatives have been synthesized. The Lewis acidity of these compounds was analyzed by the Gutmann-Beckett and fluoride ion affinity methods demonstrating the high Lewis acidity of these complexes. The bis(catecholato)germanes were utilized as Lewis acid catalysts for the hydrosilylation of aldehydes, the hydroboration of alkynes, Friedel-Crafts alkylation of alkenes, and the oligomerization of styrene …
The Coordination Chemistry And Reactivity Of Pd Phosphine 1-Azaallyl Complexes, Kyle M. Jackman
The Coordination Chemistry And Reactivity Of Pd Phosphine 1-Azaallyl Complexes, Kyle M. Jackman
Electronic Thesis and Dissertation Repository
Structurally responsive ligands (SRLs) are a class of ligands that change their coordination mode with a metal centre, which permits reactions that are difficult with non-SRLs, allow access to unique mechanisms, and allow isolation of unusual coordination complexes. The 1-azaallyl (1-AzA) family of SRLs are capable of isomerizing between η3-NCC and κ1-N modes that occupy two and one coordination sites, respectively. This thesis investigates a new class of phosphine 1^AzA (P^AzA) ligands and the reactivity of their coordination complexes with palladium.
The first-generation P^AzA ligand contains a phenyl linkage between the two heteroatoms and affords a …
Design And Surface Modification Of Noble Metal-Based Nanocatalysts, Xuchun Wang
Design And Surface Modification Of Noble Metal-Based Nanocatalysts, Xuchun Wang
Electronic Thesis and Dissertation Repository
This thesis investigates approaches to modifying the surface structure of noble metal-based nanocatalysts. Noble metal-based nanocatalysts, such as Pt and Pd, play a significant role in heterogeneous catalysis due to their capabilities in activating the cleavage or formation of chemical bonds, but still suffer from the high-cost issue and unsatisfied catalytic performance due to too strong or too weak adsorption of intermediates. Considering the surface specificity of heterogeneous catalysis, Bi, a cheap metal, was used to modify the surface of Pt- and Pd-based nanocatalysts. This thesis aims to unveil the role of Bi in improving their catalytic performance from both …
Investigating The Influence Of Synthetic Environments On The Electronic Structure And Luminescence Of Cr-Doped Zinc Gallate, Xincheng Li
Electronic Thesis and Dissertation Repository
Cr doped ZnGa2O4 (Cr-ZGO) has shown potential in the field of bioimaging. To achieve the nano-size suiting for bioimaging, Cr-ZGO is normally synthesized using a hydrothermal method. There are few studies on how the hydrothermal conditions influence the structure and optical properties of the Cr-ZGO. The first two parts of this thesis study how different hydrothermal temperatures and pH environments will affect the optical properties of Cr-ZGO by photoluminescence spectroscopy. By combining the electronic structure information extracted from X-ray absorption near-edge structures (XANES) and extended X-ray absorption fine structure (EXAFS), a relationship among hydrothermal conditions, optical properties …
Solid State Nmr Spectroscopic Characterization Of Metal Organic Frameworks, Vinicius Martins
Solid State Nmr Spectroscopic Characterization Of Metal Organic Frameworks, Vinicius Martins
Electronic Thesis and Dissertation Repository
Metal-organic frameworks are porous organic-inorganic materials that have attracted enormous attention due to their promising capabilities for several technologies, including carbon dioxide capture and storage, gas separation, and heterogeneous catalysis. The performance of MOFs for these applications is directly linked to their properties and, by extension, structures. Therefore, it is essential to understand the structure – property relationship. Solid-state NMR (SSNMR) spectroscopy is a technique that provides complementary information to X-ray diffraction-based techniques. SSNMR can provide short-range information around the NMR-active nucleus of interest. Furthermore, SSNMR can provide additional information regarding host-guest interactions and dynamics of adsorbed molecules, which play …
The Effects Of Solution Ph, Temperature And Redox Environment On Corrosion And Oxide Formation On Inconel X-750, Mohsen Bahrami
The Effects Of Solution Ph, Temperature And Redox Environment On Corrosion And Oxide Formation On Inconel X-750, Mohsen Bahrami
Electronic Thesis and Dissertation Repository
Nickel-based superalloys have a wide range of applications in different industries due to their exceptional mechanical and corrosion-resistance properties. These alloys are widely employed in the nuclear industry. Inside a nuclear reactor, these alloys are exposed to a continuous flux of gamma-radiation. When exposed to gamma-radiation, water decomposes, resulting in the production of oxidizing and reducing species. These species have a considerable effect on the redox chemistry of the solution, which controls the overall corrosion behaviour of nickel-based superalloys.
Corrosion of metals and alloys involves several elementary steps. A comprehensive understanding of these steps and how they influence each other …
Metal Ligand Cooperative Complexes For Acceptorless Dehydrogenation Of Amines, Matthew D. Hoffman
Metal Ligand Cooperative Complexes For Acceptorless Dehydrogenation Of Amines, Matthew D. Hoffman
Electronic Thesis and Dissertation Repository
Complexes of the type [M(Cp/Cp*)(MeCN)(PR2NR′2)]PF6 (M = Fe, Ru) were synthesized and/or tested towards acceptorless dehydrogenation (AD) of amines. The primary amine benzylamine can undergo AD to form a mixture of products, and a selection of catalysts were employed in an attempt to control product selectivity. As a result, trends in product distribution were observed by modifying the primary and secondary coordination spheres on the catalyst. A new complex, [Fe(Cp)(MeCN)(PPh2NPh2)]PF6 (3a) was synthesized and characterized and was found to be a completely selective dehydrogenation …
Effects Of Gamma-Radiation On The Evolution Of Copper Corrosion Dynamics In Deep Geological Repository Solution Environments, Lindsay J. Grandy
Effects Of Gamma-Radiation On The Evolution Of Copper Corrosion Dynamics In Deep Geological Repository Solution Environments, Lindsay J. Grandy
Electronic Thesis and Dissertation Repository
The Canadian plan for permanent disposal of used nuclear fuel involves a used fuel container (UFC), a carbon steel vessel with a copper coating to provide the corrosion protection. The corrosion conditions for the copper layer of the UFC are expected to involve small, stagnant water volumes, pH values between 6 and 9, and a continuous flux of γ-radiation emitted from the radionuclides trapped in the fuel matrix. While γ-radiation does not affect the copper metal directly, humid air and water will radiolytically decompose into redox-active and acidic species which will be produced at constant concentrations and can alter the …
Functional Nanoparticles: Tin Monoxide And Molybdenum Disulfide Quantum Dots On Graphene Nanosheets, Denys Vidish
Functional Nanoparticles: Tin Monoxide And Molybdenum Disulfide Quantum Dots On Graphene Nanosheets, Denys Vidish
Electronic Thesis and Dissertation Repository
Light harvesting can be referred to the use of an ensemble of different nanoparticles, or quantum dots, or other absorbers to optimize the ability to capture a given spectrum of electromagnetic radiation (for example the solar spectrum under specific atmospheric conditions) in a light-absorbing system. To this end, different nanoparticles play complementary functions within the system and absorb or scatter light at different wavelength intervals. Light harvesting finds applications in fields as diverse as solar cells, photosynthesis and photocatalysis. Graphene supporting a set of different semiconducting nanoparticles has often been proposed as light harvesters. To further this concept, my thesis …
Cyclization Of Peptide Structures By Creating Metal Foldamers Using 99m-Tc/Re(Co)3, Dhvani D. Oza
Cyclization Of Peptide Structures By Creating Metal Foldamers Using 99m-Tc/Re(Co)3, Dhvani D. Oza
Electronic Thesis and Dissertation Repository
Constrained peptides have been successful as therapeutics owing to the rigidity in their framework, allowing them to have enhanced pharmacological properties. Apart from covalent bond based cyclization, constraints can be induced by cyclization using metal coordination. The metals Re and 99mTc are one of the few metals which have not been studied in great detail for their ability to cyclize linear peptides. A tri-alanine sequence was employed in the peptide backbone due to its ability to form stable helices. In addition, another tripeptide sequence RGD, which is recognized by the integrin avb3, was also used. …
Electronic And Local Structures Of Pt-Based Bimetallic Alloy And Core-Shell Systems, Jiatang Chen
Electronic And Local Structures Of Pt-Based Bimetallic Alloy And Core-Shell Systems, Jiatang Chen
Electronic Thesis and Dissertation Repository
This thesis investigates the electronic structure of Pt for catalysis applications. The importance of the Pt 5d band is discussed in terms of the bonding capability of Pt. The oxygen reduction reaction in proton exchange membrane fuel cells is chosen as the catalytic reaction model to illustrate the effect of Pt 5d states on Pt-O interaction. Pt-based bimetallic systems are introduced as a solution for the high price and limited resources of Pt. Despite lower usage of Pt, the tuning capability to optimize the Pt 5d band in bimetallic catalysts is supposed to provide superior catalytic activity. Advanced synchrotron X-ray …
Iron(Ii) Metal-Ligand Cooperative Catalysts For Endo-Selective Intramolecular Hydrofunctionalization, Benjamin Bridge
Iron(Ii) Metal-Ligand Cooperative Catalysts For Endo-Selective Intramolecular Hydrofunctionalization, Benjamin Bridge
Electronic Thesis and Dissertation Repository
Two new cationic Fe(II) PR2NR'2 complexes, [Fe(Cp*)(PR2NPh2)(MeCN)]PF6 (R = cyclohexyl, 3a) and [Fe(Cp*)(PR2NPh2)(MeCN)]PF6 (R = phenyl, 3b), were synthesized and characterized. The catalytic activity for intramolecular hydrofunctionalization was tested using the benchmark substrate 2-ethynylaniline (EA) and both catalysts effectively produced indole (Ind). The selectivity of catalysis was also tested using 2-ethynylbenzyl alcohol (EBA) and both catalysts formed only the endo product isochromene (IC). These complexes represent the first well-defined Fe(II) catalysts that …
N-Heterocyclic Carbene Ligated Group 11 Trimethylsilylchalcogenolates: Building Blocks For Heterometallic Chalcogenide Molecules, Dickron Richard Nahhas
N-Heterocyclic Carbene Ligated Group 11 Trimethylsilylchalcogenolates: Building Blocks For Heterometallic Chalcogenide Molecules, Dickron Richard Nahhas
Electronic Thesis and Dissertation Repository
The synthesis of heterometallic chalcogenide molecules requires the continued investigation into the appropriate reagents necessary to introduce metal – chalcogen bonds in a controlled fashion. Trimethylsilyl metallochalcogenolates (MESiMe3) act as synthons introducing “ME–“ in solution upon reacting with an appropriate ternary metal reagent, MX (X= halide, acetate, etc.). Recent work makes use of N–heterocyclic carbenes (NHCs) as a class of ancillary ligand that can stabilize these reagents and the heterometallic chalcogenide molecules obtained with them. Building on previous work, this thesis describes the synthesis of group 11 trimethylsilyl metallochalcogenolates stabilized by bis–1,3–tritylimidazole–2–ylidene (abbreviated ITr) …
High-Pressure Studies On The Transition From Red Phosphorus To Black Phosphorus, Heng Xiang
High-Pressure Studies On The Transition From Red Phosphorus To Black Phosphorus, Heng Xiang
Electronic Thesis and Dissertation Repository
Black phosphorus (BP) is a promising material in many research fields. However, the transition process from amorphous red phosphorus (ARP) is elusive and hence hinders large scale synthesis and applications. This work describes the application of the high-pressure method to study the transition process from ARP to BP.
In this thesis, the following three objectives were achieved: (1) to understand the mechanism of the transition, (2) to facilitate the synthesis of BP by taking the advantage of less pure ARP, (3) to propose new methods of synthesizing BP-based materials, such as the moderately oxidized BP and the black phosphorus/ amorphous …
Investigations Of The High Pressure Effects On Structural Properties And Co2 Adsorption Performance Of Mofs Using Vibrational Spectroscopy, Shan Jiang
Electronic Thesis and Dissertation Repository
The pre- and post-combustion carbon dioxide capture has drawn much attention in the past few decades owing to the increasing concentration of CO2 in the atmosphere. Among all the potential solid adsorbents for CO2 capture, metal-organic frameworks (MOFs) are a promising class of materials due to their large surface areas, high tunability and their high selectivity for gas adsorption applications. It has been widely demonstrated that the application of high external pressure in gigapascal level can substantially tune the structure, pore size and opening of porous material. Consequently, the structural, as well as gas adsorption properties of these …
Progress Toward Durable Icephobic Materials, Matthew J. Coady
Progress Toward Durable Icephobic Materials, Matthew J. Coady
Electronic Thesis and Dissertation Repository
Ice accumulation is a major engineering challenge in many fields including aerospace, power generation, transportation, and infrastructure. A variety of solutions are being researched to address this challenge. Perhaps the most promising method of combating ice accumulation is by applying coatings with low values of interfacial ice adhesion strength, τice. Icephobic materials are those with ice adhesion below 100 kPa, and it has been shown that passive delamination can occur on surfaces with τice below 20 kPa. While various low adhesion surfaces have been prepared, durability concerns pervade applications where surfaces experience repeated icing or freeze-thaw cycles, …
Zinc–Phosphorus Clusters For Solution Synthesis Of Zinc Phosphide Nanoparticles, Kyungseop Lee
Zinc–Phosphorus Clusters For Solution Synthesis Of Zinc Phosphide Nanoparticles, Kyungseop Lee
Electronic Thesis and Dissertation Repository
Synthesis of zinc phosphide (Zn3P2) nanoparticles is an emerging topic of investigation as Zn3P2 is a candidate material for the next generation solar cells. Despite the early discovery of its favorable electronic properties that are well-suited for photovoltaic applications, a major focus of synthetic strategy was with vapor/chemical deposition methods. Solution methods with greater control over size, crystal structure and composition at a lower production cost, has been underdeveloped in comparison. In this context, this thesis describes the synthesis, characterization and reactivity of zinc phosphido clusters: [Zn2(μ-PPh2)2(PPh …
Methodologies For Metal Functionalization Of Phosphorus Based Photopolymer Networks, Vanessa Béland
Methodologies For Metal Functionalization Of Phosphorus Based Photopolymer Networks, Vanessa Béland
Electronic Thesis and Dissertation Repository
Photopolymer networks with phosphonium cation, alkyl phosphine and olefin functionality were designed, synthesized and functionalized with metals by metathesis, coordination and hydrometallation reactions, respectively. The materials were strategically designed so that the metal functionalization step could be monitored and quantified. In some cases, this involved characterization by IR, NMR, or X-ray spectroscopic techniques, or by comparison to molecular analogues. It was found that by using a bi-functional photopolymer network, the material could be bi-metallized by orthogonal mechanisms. All metallized polymer networks were tested for their suitability as precursors to metal-containing ceramics. The polymers were pyrolyzed, and on analysis it was …
The Reactivity Of Ditetrelenes Towards Organophosphorus Oxides, Maissa Belcina
The Reactivity Of Ditetrelenes Towards Organophosphorus Oxides, Maissa Belcina
Electronic Thesis and Dissertation Repository
The reactivity of tetramesityldisilene 4 and tetramesityldigermene 5 towards organophosphorus oxides was explored in this thesis. The reaction of dialkyl and diarylphosphine oxides and phosphites with ditetrelenes 4 and 5 resulted in a 1,3-addition to form diorganodisilyl and digermyl phosphinites 27, 28, 31, 32 and disilyl phosphites 35 and 36. The 1,3-addition resulted in a mild two electron reduction of the P(V) centre of the phosphine oxide and phosphite to a P(III) centre in the products, without the use of heat or a catalyst. The reaction of organophosphorus oxides provides another example of a main group …
Synthesis, Characterization, And Applications Of Group 13 And 14 Complexes Of Chelating Formazanate Ligands, Ryan R. Maar
Synthesis, Characterization, And Applications Of Group 13 And 14 Complexes Of Chelating Formazanate Ligands, Ryan R. Maar
Electronic Thesis and Dissertation Repository
This thesis describes the synthesis and characterization of group 13 (boron and aluminum) and group 14 (silicon, germanium, and tin) complexes supported by chelating formazanate [R1-N-N=C(R3)-N=N-R5]‒ ligands. The resulting complexes are redox-active and often luminescent. Chapters two to four describe the synthesis and characterization of boron formazanate adducts. The work in these chapters demonstrates that through structural modification of the formazanate ligand, solid-state- and NIR photoluminescence can be achieved. Furthermore, the formation of an oxoborane (B=O) afforded a highly photoluminescent formazanate adduct due to the structural rigidity imposed by the B=O bond. These …
Non-Traditional Metallation Of Metallothioneins With Xenobiotic Therapeutic Metals, Daisy L. Wong
Non-Traditional Metallation Of Metallothioneins With Xenobiotic Therapeutic Metals, Daisy L. Wong
Electronic Thesis and Dissertation Repository
The rise of the Anthropocene has seen more global pollution than before in history. With the explosion of consumer electronics in the last half century, the rise of metal pollution from their extraction and disposal results in the unnatural introduction of heavy and rare metals into the ecosystem. Organisms have a metal defense protein, metallothionein, which has multiple roles in essential metal regulation and protection against minimal toxic metal exposure. However, these modern heavy metals prominent in electronics are not found biologically and their interactions in the body are generally unknown. Some of these metals are employed as therapeutic agents …
Development Of In Situ Forming Hydrogels For Intra-Articular Drug Delivery, Andy Prince
Development Of In Situ Forming Hydrogels For Intra-Articular Drug Delivery, Andy Prince
Electronic Thesis and Dissertation Repository
Hydrogels are 3-dimensional crosslinked polymer networks that can absorb significant amounts of water. The physical properties associated with hydrogels affords them resemblance to biological tissues making them good candidates for biomedical applications. Many pharmaceuticals, specifically non-steroidal anti-inflammatory drugs (NSAIDs), have poor aqueous solubility, which limits their bioavailability and efficacy. People suffering from chronic osteoarthritis (OA) are required to frequently take large doses to mitigate pain, which can lead to serious side effects. Hydrogels are good strategies to deliver NSAIDs via articular injection because they can form solid gels in situ. This thesis describes the synthesis, formulation, mechanical testing, in …
Pressure Tuning Of Energy Storage Materials Probed By In-Situ Vibrational Spectroscopy And Synchrotron Radiation, Pan Wang
Electronic Thesis and Dissertation Repository
Clean and renewable energy has drawn much attention recently due to the increasing demand for more energy and environmental issues. New materials have been developed and the improved performance of such materials have been achieved in the past decades. It has been proved that application of external high pressure can significantly tune the structure of materials. Consequently, the properties of the materials could also be modified. Therefore, in this thesis, we focused on the high-pressure studies of two classes of energy storage materials, hydrogen storage materials and solar cell materials. Ammonia borane (AB) has been extensively investigated as an excellent …
Exploring The Chemistry Of Asymmetric Phosphines & Phosphinidene Sulfides, Taylor E. Pritchard
Exploring The Chemistry Of Asymmetric Phosphines & Phosphinidene Sulfides, Taylor E. Pritchard
Electronic Thesis and Dissertation Repository
The field of low-coordinate main group chemistry has seen huge development in the last 30 years, with novel compounds that demonstrate unique structures and reactivity. Isolation of these species has relied on thoughtfully designed substituents normally containing substructure steric bulk. The area of phosphinidene chalcogenide isolation and transfer remains poorly understood by comparison. In this context, the major focus of thesis was on the development of a room-temperature method for the transfer of RP=S moieties with and without sterically demanding substituents. The preparation and complete characterization of new asymmetric phosphines with m-terphenyl ligands was also reported. In Chapter 2, …
Design, Synthesis, And Oxidation Reactivity Of Palladacyclic Complexes Containing N-Donor Ligands, Ava Behnia
Design, Synthesis, And Oxidation Reactivity Of Palladacyclic Complexes Containing N-Donor Ligands, Ava Behnia
Electronic Thesis and Dissertation Repository
This thesis describes the synthesis and reactivity of complexes containing the cycloneophyl-Pd(II) group, PdCH2CMe2C6H4, in combination with N-donor ligands. These compounds contain both alkyl- and arylpalladium bonds and the selectivity of bond cleavage in reactions with oxidants and protic reagents is studied, often involving oxidative addition and reductive elimination reaction sequences.
The diimine ligand in [Pd(CH2CMe2C6H4)(MesN=CH-CH=NMes)] does not support formation of stable palladium(IV) complexes, but reactions with Br2 or I2 lead to reductive elimination by C-C bond formation of 1,1-dimethylcyclobutabenzene while …