Late First-row Transition Metals in Weak Ligand Fields - Correlating High-Spin Electronic Structure and Reactivity PDF Download
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Author: Graham Thomas Sazama
Publisher:
ISBN:
Category :
Languages : en
Pages :
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High spin has been shown to be necessary for optimal reactivity of transition metal complexes toward the activation and functionalization of C-H bonds. This thesis presents our examination of the weak-field, tripodal, trianionic tris(pyrrolyl)ethane (tpe) ligand and its complexes.
Author: Graham Thomas Sazama
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Book Description
High spin has been shown to be necessary for optimal reactivity of transition metal complexes toward the activation and functionalization of C-H bonds. This thesis presents our examination of the weak-field, tripodal, trianionic tris(pyrrolyl)ethane (tpe) ligand and its complexes.
Author: Leslie E. Orgel
Publisher:
ISBN:
Category : Chemistry, Physical and theoretical
Languages : en
Pages : 184
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Author: David Michael P. Mingos
Publisher: Springer Science & Business Media
ISBN: 3642273696
Category : Science
Languages : en
Pages : 227
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Book Description
J.P. Dahl: Carl Johan Ballhausen (1926–2010).- J.R. Winkler and H.B. Gray: Electronic Structures of Oxo-Metal Ions.- C.D. Flint: Early Days in Kemisk Laboratorium IV and Later Studies.- J.H. Palmer: Transition Metal Corrole Coordination Chemistry. A Review Focusing on Electronic Structural Studies.- W.C. Trogler: Chemical Sensing with Semiconducting Metal Phthalocyanines.- K.M. Lancaster: Biological Outer-Sphere Coordination.- R.K. Hocking and E.I. Solomon: Ligand Field and Molecular Orbital Theories of Transition Metal X-ray Absorption Edge Transitions.- K.B. Møller and N.E. Henriksen: Time-resolved X-ray diffraction: The dynamics of the chemical bond.
Author: Vinod Jena
Publisher: Lulu.com
ISBN: 1329059875
Category : Reference
Languages : en
Pages : 93
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Book Description
This books will provides a conceptual parts of Electronic spectra of various transition metal complexes, which is useful for various competitive examinations.
Author: Stefanie A. Cantalupo
Publisher:
ISBN:
Category :
Languages : en
Pages : 440
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Book Description
Abstract: Seven homoleptic first-row transition metal complexes were prepared with the perfluorot-butoxide ligand with three- and four-coordinate geometry. The compounds were prepared via metathesis reactions with the form [M(OC 4F9)3]-, M = Mn (1), Fe (2), Co (5), and Zn (7); [M(OC 4F9)4]n-, M = Fe (4), Co (6); and the THF adducts [M(THF)(OC4F 9)3]-, M = Co (5-THF), and Zn (7-THF). The complexes were synthesized and structurally characterized. Spectroscopic characterization with UV-vis, NMR, and IR will be discussed. Cyclic voltammetry studies of 5 and 6 in conjunction with UV-vis data show the presence of an equilibrium between the three-and four-coordinate complexes with ligand association and dissociation. Using the bidentate perfluorinated pinacolate ligand, ddfp, three complexes were prepared as [M(ddfp)2]2-, in which M = Fe ( 8), Co (9), and Zn (10). Complexes 8 and 9 have square-planar geometry and are high-spin. The magnetism was studied both in solution and the solid state. The combination of geometry and spin-state is rare for {MO4} complexes and 9 is the first example of {CoO4} with this combination, and 8 is the second example of this combination in an {FeO 4} system. A five-coordinate Co complex was also structurally characterized (9-OH2). A family of heteroleptic complexes of the form [Fe(X)(OC4F 9)3]- in which X = Cl (11), Br (12), or pyridine (13), and [M(py)(ddfp)2] 2- for M = Co (14), and Fe (15), were prepared and some were structurally characterized. Analytical data suggests the formation of an iron-amide complex, [Fe(HN(C6H5)(ddfp)2] 3-, (16), capable of further reactivity. The synthesis, characterization, and preliminary reactivity studies will be discussed. Two iron aryloxide complexes were synthesized with the pentafluorophenolate ligand, [Fe(OArF)4]2-, (17 ) and [OArF)3Fe(u2-OAr F)2Fe(OArF)3]2-, (18). The FeIII complex was formed as a result of presumed ligand oxidation and dissociation, highlighting the vulnerability of aryloxide ligands. A series of isotopically labeled compounds containing a short, strong hydrogen bond were prepared and characterized for neutron diffraction experiments. The compounds, [Cp2Co][D(OAr')], (19) and d10-[Cp2Co][H(OAr')], (20), were prepared with the partially fluorinated OAr' ligand, bis-(3,5-trifluoromethyl)phenoxide. The synthesis and characterization of these compounds will be discussed.
Author: David Shaffer
Publisher:
ISBN: 9781267646378
Category :
Languages : en
Pages : 233
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Book Description
The overarching theme of the work herein is the investigation of the effects of ligand electronics on the electronic structure and reactivity of non-innocent late transition metal complexes. Chapter 2 describes the electronic structure of (nacnacR[supercript]) Rh II[superscript] (phdisq) (nacnacR[superscript] = CH[C(R)(N-i [superscript] Pr2 C6 H3)]2, -[superscript], R = CH3, CF3; phdisq = 9,10-phenanthrenediiminosemiquinone *[superscript]-[superscript]), which incorporates both a reducible diimine ligand and a reducing [beta]-diketiminate ligand. The complex is assigned as having highly delocalized, closed shell frontier orbitals. One-electron oxidation of (nacnacCH3[superscript]) RhII[superscript] (phdisq) produces a delocalized ligand-based radical, while one-electron reduction gives (nacnac CH3[superscript]) RhII[superscript]) (phda). Chapter 3 studies the oxidative addition of halogen substrates to (nacnacR[superscript]) Rh(phdisq). Chlorine and bromine are observed to add in a normal trans fashion, but the addition of iodine is found to be dependent on the electronic properties of the ligands, forming either an [eta]1 -I2 complex or the oxidative addition product. Chapter 4 reports the reactions of (nacnacCH3[superscript])Rh(phdisq) with haloacids. The addition of HCl quickly produces the product [(nacnacH[superscript]CH3[superscript] RhCl2 (phdaH2)]+[superscript] (phdaH2 = 9,10-phenanthrenediamine), which is the result of protonation of the (nacnacCH3[superscript]) ligand, oxidative addition to the rhodium center, and hydrogenation of the phdi ligand. This reaction is reversible, and the deprotonated (nacnacCH3[superscript])RhCl2 (phdaH2) is also isolable but undergoes slow disproportionation. All phdaH2 complexes are dehydrogenated by oxygen to give the corresponding phdi products. Chapter 5 examines the differences between (nacnacCH3[superscript])Co(phdisq) and (nacnacCH3[superscript])Rh(phdisq). The solid state structures are completely analogous, suggesting analogous electronic ground states. Differences in the solution spectroscopic characterization between the rhodium and cobalt complexes suggest the existence of a thermally accessible triplet state for (nacnacCH3[superscript])Co(phdisq). Chapter 6 addresses the question of how the introduction of a reducible ligand will affect the electrocatalytic potential of a catalyst for proton reduction. The complexes (adi)M(bdt) (M = Ni, Co; adi = N-N'-bis(2,4,6-trimethylphenyl)-acenapthene-1,2-diimine, bdt = 1,2-benzenedithiolate2-[superscript] are described, and the cobalt complex is evaluated as an electrocatalyst for H+[superscript] reduction. Results indicate that the [eta]-acidic nature of the adi ligand makes the cobalt center less basic, thus reducing its catalytic efficiency. Chapter 7 compares tungsten complexes of the well-known redox active bis(3,5-di- tert- butyl-phenolate)amido3-[superscript] ligand (ONO3-[superscript]) and the novel bis(4-methyl-thiophenolate)amido3-[superscript] (SNS3-[superscript]) ligand. While W(ONO)2 is found to be an `innocent' tungsten(VI) complex, W(SNS)2 is described as tungsten(IV) with partially oxidized (SNS) ligands. W(SNS)2 has a highly distorted geometry that is ascribed to [eta]-[eta] interactions in the solid state.
Author: Marcel Swart
Publisher: John Wiley & Sons
ISBN: 1118898303
Category : Science
Languages : en
Pages : 472
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Book Description
It has long been recognized that metal spin states play a central role in the reactivity of important biomolecules, in industrial catalysis and in spin crossover compounds. As the fields of inorganic chemistry and catalysis move towards the use of cheap, non-toxic first row transition metals, it is essential to understand the important role of spin states in influencing molecular structure, bonding and reactivity. Spin States in Biochemistry and Inorganic Chemistry provides a complete picture on the importance of spin states for reactivity in biochemistry and inorganic chemistry, presenting both theoretical and experimental perspectives. The successes and pitfalls of theoretical methods such as DFT, ligand-field theory and coupled cluster theory are discussed, and these methods are applied in studies throughout the book. Important spectroscopic techniques to determine spin states in transition metal complexes and proteins are explained, and the use of NMR for the analysis of spin densities is described. Topics covered include: DFT and ab initio wavefunction approaches to spin states Experimental techniques for determining spin states Molecular discovery in spin crossover Multiple spin state scenarios in organometallic reactivity and gas phase reactions Transition-metal complexes involving redox non-innocent ligands Polynuclear iron sulfur clusters Molecular magnetism NMR analysis of spin densities This book is a valuable reference for researchers working in bioinorganic and inorganic chemistry, computational chemistry, organometallic chemistry, catalysis, spin-crossover materials, materials science, biophysics and pharmaceutical chemistry.
Author: Jon A. McCleverty
Publisher:
ISBN: 9780191992971
Category : Transition metals
Languages : en
Pages : 0
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Book Description
'Chemistry of the First Row Transition Metals' introduces this field of chemistry. The reactivity and structural properties of first-row transition metals and their compounds depend on the electronic configuration of the d electrons of the metal. The book describes the most significant structures, reactions, and other important properties of co-ordination, organometallic and solid-state compounds, and also sketches the role of first-row transition metals in biology.
Author: Metallurgical Society of AIME. Institute of Metals Division
Publisher:
ISBN:
Category : Chemistry
Languages : en
Pages : 272
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Author: Christine M. Morales
Publisher:
ISBN:
Category :
Languages : en
Pages : 344
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Book Description
