Download or read book Synthesis Characterization and Reactivity of First Row Dipyridylazaallyl Transition Metal Complexes written by Brenda Frazier and published by . This book was released on 2010 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Synthesis Reactivity and Catalytic Applications of Two Coordinate First Row Transition Metal Complexes written by Michael Isaac Lipschutz and published by . This book was released on 2015 with total page 139 pages. Available in PDF, EPUB and Kindle. Book excerpt: Recently, the development of more sustainable catalytic systems based on abundant first-row metals, especially nickel, for organic transformations has attracted significant interest. This thesis describes the development of new synthetic methods for the preparation of two-coordinate complexes of a variety of first row transition metals. The physical and spectroscopic properties of these complexes are discussed and the reactivity and catalytic applications of these compounds are also explored. Species of this type are found to catalyze a variety of useful organic transformations using inexpensive metals and ligands.
Download or read book The Synthesis Characterization and Reactivity of First row Late Transition Metal Complexes Containing Tridentate Pincer type N heterocyclic Phosphenium Ligands written by Sadie E. Knight and published by . This book was released on 2015 with total page 276 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Synthesis Characterization and Reactivity of Heterobimetallic Transition Metal Complexes written by David Morris Hamilton and published by . This book was released on 1981 with total page 206 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Reactivity and Thermochemistry of First row Transition Metal Complexes with Stable Organic Radicals written by Thomas R. Porter and published by . This book was released on 2014 with total page 179 pages. Available in PDF, EPUB and Kindle. Book excerpt: Reactions involving transition metals and organic free radicals are critically important in a variety of chemical and biological processes. Because of their prevalence, there is a fundamental interest in better understanding these types of reactions to fully realize their potential for new applications. The work presented in this dissertation describes the free radical reactivity and thermochemistry of several different transition metal systems with stable organic radicals. Chapter 1 provides an introduction to transition metal reactivity involving organic free radicals. Chapter 2 describes the catalytic disproportionation of a hydroxylamine by (TMP)Fe[superscript III]-OH (TMP = meso-tetramesityl porphyrin) and some of the radical reactions that make up the catalytic cycle. Chapter 3 describes the preparation, structural characterization and thermochemistry of a previously unreported stable organic radical, [superscript t]Bu2NPArO* (2,6-di-tert-butyl-4-(4'-nitrophenyl)phenoxyl). Chapter 4 describes the preparation of several [Tp[superscript tBu]Cu[superscript II]]+ (Tp[superscript tBu] = hydro-tris(3-tert-butyl-pyrazolyl)borate) and [Tp[superscript tBuMe]Cu[superscript II]]+ (Tp[superscript tBu]Me = hydro-tris(3-tert-butyl-5-methyl-pyrazolyl)borate) alkoxide compelxes as models for potential intermediates in copper/radical alcohol oxidation catalysis. Treating these complexes with stable radicals such a [superscript t]Bu3ArO* (2,4,6-tri-tert-butyl-phenoxyl) did not result in alkoxide oxidation despite having a large driving force. From these studies, we conclude driving force is not a primary predictor for copper/radical alcohol oxidation. Chapter 5 discusses the coordination chemistry of [Tp[supercscript tBu]Cu[superscript II]]+ and [Tp[superscript tBu]Zn[superscript II]]+ with 4-nitro-phenols. With the bulky 2,6-disubstituted 2,6-di-tert-butyl-4-nitro-phenoxide, coordination to either metal occurs through a nitronate resonance form. The 2,6-unsubstituted 4-nitro-phenol binds through the phenoxide resonance form. Chapter 6 highlights the large kinetic barrier for ketone reduction or oxidation by titanocene(III/IV) and the hydrogen atom donor/acceptor, [superscript t]Bu3ArO(-H). Finally, Chapter 7 describes the selective and stoichiometric reduction of aromatic and aliphatic nitro groups by photoreduced titanium dioxide nanoparticles in acidic aqueous solutions. From thermochemical analysis, it is likely that these reactions proceed through a rate determining H+/e- transfer.
Download or read book The Molecular Structure and Characterization of Some First Row Transition Metal Complexes with Monodentate Ligands written by William John Rozell and published by . This book was released on 1981 with total page 340 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Transition Metal Complexes with Di pentadienyl Ligands written by Weiqing Weng and published by . This book was released on 1991 with total page 424 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Synthesis Characterization and Reactivity of Ylidyne and Ylido Complexes Supported by Scorpionato Ligands written by Priyabrata Ghana and published by Springer. This book was released on 2019-01-01 with total page 345 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book explores the development of the first open-shell heavier tetrylidyne complexes featuring a tetrel-centered unpaired electron, and unprecedented metallatetrylidynes containing a multiply-bonded, linear-coordinated single heavier tetrel atom embedded between two metal centers. The chemistry of compounds featuring triple bonds of the heavier Group-14 elements Si–Pb with transition metals is a very challenging research area, which combines modern molecular main-group element with transition-metal chemistry, and is of fundamental importance for the understanding of chemical bonding. During the last 15 years, the research in this area has witnessed considerable progress in isolating a series of closed-shell tetrylidyne complexes. However, despite numerous attempts, open-shell tetrylidyne complexes and heavier group 14 element congeners of metallacarbynes and carbide complexes remained inaccessible. In this book, readers will find more about the reactivity studies of these novel complexes that uncovered a plethora of exceptional products, including a novel m3-silicido complex, the first dimetallasilacumulene with a linear, two-coordinated single silicon atom and the first compounds of planar tetracoordinated silicon (ptSi) (Anti-van’t Hoff-Le Bell Silicon). Readers will also learn about the isolation and full characterization of the first room-temperature stable disilavinylidene, a silicon analogue of the very reactive vinylidenes (R2C=C:), and the first intermetallic plumbylidyne ligand transfer reactions.
Download or read book Synthesis and Characterization of Complexes of First Row Transition Metals with a Linear Potentially Hexadentate Schiff Base Ligand written by Justin C. Biffinger and published by . This book was released on 1999 with total page 152 pages. Available in PDF, EPUB and Kindle. Book excerpt: Describes the synthesis and structure of mononuclear M(III) complexes and what factors control the stereochemistry.
Download or read book Studies of D 5 d 9 First Row Transition Metal and Tin Complexes Containing 1 aza allyl Or Beta diketiminato Ligands written by John Richard Severn and published by . This book was released on 1999 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Pentadienyl Compounds of 1st 2nd and 3rd Row Transition Metals of Groups 4 5 6 and 8 written by Lothar Stahl and published by . This book was released on 1988 with total page 642 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Reactions of First row Transition Metal Complexes in Bis alkoxide Ligand Environments with Diazoalkanes written by Amanda Grass and published by . This book was released on 2020 with total page 231 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation focuses on the design and reactions of novel late transition metal carbene complexes featuring alkoxide ligand environments. The high-valent cobalt carbene Co(OR)2(=CPh2) (OR = OCtBu2Ph), featuring short Co=C bond of 1.773(3) ©5, was previously reported from the reaction of Co(OR)2(THF)2 with diphenyldiazoalkane. Magnetic and spectroscopic (EPR) studies demonstrated Co(OR)2(=CPh2) to be a low-spin S = ℗ư complex. Computational studies, in agreement with experimental data, suggested that the electronic structure of Co(OR)2(=CPh2) lies between intermediate spin Co(III) anti-ferromagnetically coupled to a carbene radical and a Co(IV) alkylidene. This dissertation began with investigation of this complex in carbene transfer reactivity. Stoichiometric ketenimine formation occurs upon reaction with various isocyanides CNR0́ø (CNR0́ø =2,6-dimethylphenyl isocyanide, 4-methoxyphenyl isocyanide, 2-chloro-6-methylphenyl isocyanide, adamantyl isocyanide). The reaction is accompanied by the formation of a cobalt bis(alkoxide) bis(isocyanide) complexes Co(OR)2(CNR)2, which were independently synthesized and characterized. Excess isocyanide was required to form ketenimine due to formation of the bis(isocyanide) complex. DFT calculations suggest the mechanism proceeds through isocyanide binding to cobalt, in contrast to nucleophilic attack at the carbene carbon. This is followed by intramolecular insertion into the Co-carbene bond to form the ketenimine complex. Dissociation of free ketenimine from cobalt then leads to the bis(isocyanide) complex. Catalytic formation of ketenimines was investigated at room temperature by exposing the mixtures of the carbene precursors and isocyanides to Co(OR)2(THF)2. The carbene precursors investigated included both diazoalkane (diphenyldiazomethane) and diazoesters (methyl phenyldiazoacetate, and ethyl diazoacetate).
Download or read book Synthesis Characterisation and Thermal Analysis of Some First Row Transition Metal Complexes and Their Application in Polymer Systems written by Iain J. Wood and published by . This book was released on 1995 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Synthesis and Reactivity of Dinitrogen Oxo and Nitrido Complexes of First Row Transition Metals Supported by Hydrotris pyrazolyl borate Ligands written by Daniel Clayton Cummins and published by . This book was released on 2018 with total page 281 pages. Available in PDF, EPUB and Kindle. Book excerpt: When 9 is reacted with single oxygen atom transfer reagents the novel bridging oxo complex in the form of [TpFc,MeFe] 2(μ2-η1:η1-O) (16) is produced. 16 is only the second instance of such a FeII-O-FeII compound to have been isolated and structurally characterized. In the effort to produce additional chalcogenide compounds the complexes TpFc,MeFeOCPh3 (13) and TpFc,MeFeSCPh3 (14) were produced by salt metathesis with 3. The reaction of 14 with KH in the presence of 18-crown-6 to produce a bridging sulfide, [Tp Fc,MeFe]2(μ2-η1:η 1-S) (15). Attempts to produce imide compounds to act as isoelectronic models for terminal oxo compounds by reacting organic azides with 9 and 10 resulted in the production of tetrazene complex TpFc,MeCoN4Bn2 (17), as well as metallated azides TpFc,MeFeN3 (20) and TpFc,MeCoN3 (21).
Download or read book Synthesis and Reactivity of Transition Metal Complexes Bearing the Tridentate Bis 2 mercapto p tolyl amine SNS H 3 Ligand written by Kyle Evan Rosenkoetter and published by . This book was released on 2017 with total page 196 pages. Available in PDF, EPUB and Kindle. Book excerpt: The work described herein focuses on the synthesis and characterization of new heterobimetallic complexes containing the redox-active W[SNS] 2 metalloligand and investigation into their electronic properties and reactivity. Most recent studies have explored the redox nature of the [SNS]H 3 scaffold through the synthesis and reactivity of a novel set of square-planar nickel complexes.Chapters 2 and 3 describe a modular synthetic approach towards generating a new series of heterobimetallic complexes with the general formula W[SNS]2M(L) ([SNS] = bis(2-mercapto- p-tolyl)amine; M = Ni, Pd, or Pt; and L = dppe, depe, dmpe, dppp, PR'2NRPR'2 (R = phenyl, benzyl; R'=phenyl), DPEphos or dppf). The complexes were prepared by a salt metathesis of Cl2MII(L) with the previously reported W[SNS]2 coordination complex under reducing conditions. X-ray diffraction analysis revealed interesting coordination geometries about the appended Group 10 metal centers moving from Pt and Pd (pseudo-square planar) to the first row Ni (pseudo-tetrahedral) analogue. These complexes demonstrate formal metal--metal bond formation across the series with a tunable first oxidation potential up to 600 mV.Chapter 4 investigates the use of W[SNS]2Ni(dppe) as a catalyst for the electrochemical reduction of protons to hydrogen. This complex was found to catalytically generate hydrogen with an overpotential of 700 mV, a TOF of 14 sec--1, and a Faradaic yield of 80 +/- 3 % using 4-cyanoanilinium tetrafluoroborate in non-aqueous solutions.Chapter 5 demonstrates the effect of exchanging the nickel center of the heterobimetallic complexes discussed in Chapters 2 and 3 with other first row transitions metal ions (i.e. cobalt and copper). Analysis into the observed metal--metal distances reveal stark differences across the series. Additionally, the copper ion containing complexes demonstrate dynamic behavior in solution.Chapter 6 investigates the synthesis and reactivity of a series of monomeric square-planar nickel complexes of the [SNS] scaffold to demonstrate the ligand as redox, proton, and hydrogen atom non-innocent.Appendix A illustrates the electrochemical responses observed for the monoanionic complexes from Chapter 6 in the presence of CO2 and CO. Appendices B and C describe the synthesis and characterization of a five-coordinate cobalt and a heterotrimetallic tungsten-nickel complex, respectively.
Download or read book Synthetic and Spectroscopic Investigations of the 1 3 Dipyridylazaallyl smif Anion with 2nd and 3rd Row Transition Metals and a Series of Diarylimine Iron Bisphosphine Complexes that Selectively Extract Dinitrogen from Air written by Erika Rose Bartholomew and published by . This book was released on 2013 with total page 194 pages. Available in PDF, EPUB and Kindle. Book excerpt: Aryl-based chelates containing oxazoline or imine donors were synthesized, and their reactivity with 1st -row transition metals were investigated in an attempt to generate metal complexes containing strong field ligands. Successful arylation of nickel was accomplished with a bis-methylated benzyl-oxazoline aryl anion. The reactivity of the dipyridyl imine ligand, 1,3-di-(2-pyridyl)-2-azapropene (smifH), was investigated with Ru, Rh, Ir, Mo and Pd. The d6 bis-smif metal complexes were successfully generated with Ru, Rh and Ir, while carbon-carbon bond formation was observed with Mo and Pd. Treatment of cis-(Me3P)4FeMe2 with ortho-substituted diarylimines afforded two equivalents of CH4, PMe3, and generated tris-PMe3 Fe(II) complexes. Exposure to O2 caused rapid degradation, but substitution of the unique PMe3 with N2 occurred upon exposure to air or N2, yielding iron-dinitrogen compounds; CO, CNMe and N2CPh2 derivatives were also prepared. Dihydrogen or ammonia binding was found comparable to N2, while PMe3 and pyridine adducts were unfavorable. Protolytic conditions were modeled using primary acetylenes as weak acids, and trans-{[kappa]-C, N-(3,4,5-(F)3-C6H2)CH2N=CH(3,4,6-(F)3-C6H-2-yl)}Fe(PMe3)3(CCR) (R = Me, Ph) were generated from tris-PMe3 complexes. Reactions of tris-PMe3 Fe(II) with N2O or tosyl azide generated iron-dinitrogen complexes and Me3PO or Me3P=N(SO2)tol, respectively. Calculations revealed Fe-N2 to be thermodynamically and kinetically favored over the calculated Fe(III) superoxide complex.
Download or read book Inorganic Syntheses written by Philip P. Power and published by John Wiley & Sons. This book was released on 2018-07-06 with total page 288 pages. Available in PDF, EPUB and Kindle. Book excerpt: The newest volume in the authoritative Inorganic Syntheses book series provides users of inorganic substances with detailed and foolproof procedures for the preparation of important and timely inorganic and organometallic compounds that can be used in reactions to develop new materials, drug targets, and bio-inspired chemical entities.
