Structure and Reactivity of Low-coordinate First-row Transition Metal Complexes PDF Download
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Author: Oliver Hemming
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Author: Oliver Hemming
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Author: Jessica Nicole Boynton
Publisher:
ISBN: 9781321210804
Category :
Languages : en
Pages :
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The research in this dissertation is focused on the synthesis, structural, and magnetic characterization of two-coordinate open shell (d1-d4) transition metal complexes. Background information on this field of endeavor is provided in Chapter 1. In Chapter 2 I describe the synthesis and characterization of the mononuclear chromium (II) terphenyl substituted primary amido complexes and a Lewis base adduct. These studies suggest that the two-coordinate chromium complexes have significant spin-orbit coupling effects which lead to moments lower than the spin only value of 4.90 [mu]B owing to the fact that [lambda] (the spin orbit coupling parameter) is positive. The three-coordinated complex 2.3 had a magnetic moment of 3.77 [mu]B. The synthesis and characterization of the first stable two-coordinate vanadium complexes are described in Chapter 3. The values suggest a significant spin orbital angular momentum contribution that leads to a magnetic moment that is lower than their spin only value of 3.87 [mu]B. DFT calculations showed that the major absorptions in their UV-Vis spectra were due to ligand to metal charge transfer transitions. The titanium synthesis and characterization of the bisamido complex along with its three-coordinate titanium(III) precursor are described in Chapter 4. Compound 4.1 was obtained via the stoichiometric reaction of LiN(H)AriPr 6 with the Ti(III) complex TiCl3 *2NMe3 in trimethylamine. The precursor 4.1 has trigonal pyramidal coordination at the titanium atom, with bonding to two amido nitrogens and a chlorine as well as a secondary interaction to a flanking aryl ring of a terphenyl substituent. Compound 4.2 displays a very distorted four-coordinate metal environment in which the titanium atom is bound to two amido nitrogens and to two carbons from a terphenyl aryl ring. This structure is in sharp contrast to the two-coordinate linear structure that was observed in its first row metal (V-Ni) analogs. The synthesis and characterization of mononuclear chromium(II) terphenyl primary substituted thiolate complexes are described in Chapter 5. Reaction of the terphenyl primary thiolate lithium derivatives LiSAriPr4 and LiSArMe6 with CrCl2THF2 in a 2:1 ratio afforded complexes 5.1 and 5.2, which are the very rare examples of chromium(II) thiolates with quasi-two-coordination at the metal center. Both deviate from linearity and have S-Cr-S angles of 111.02(3)° and 107.86(3)° with secondary Cr-C(aryl ring) interactions of ca. 2.115 Å and 1.971 Å respectively. The initial work on titanium and vanadium terphenyl thiolates is described in Appendix I and II. In Chapter 6 I show that the reaction of K2COT (COT= 1,3,5,7-cyclooctatetraene, C8H8) with an aryl chromium(II) halide gave (CrAriPr4)2([mu]2-n3:n4-COT) (6.1) in which a non-planar COT ring is complexed between two CrAriPr4 moieties -- a configuration previously unknown for chromium complexes of COT. OneCr2+ ion is bonded primarily to three COT carbons (Cr--C= 2.22-2.30 Å ) as well as an ipso carbon (Cr-C= ca. 2.47 Å) from a flanking aryl ring of its terphenyl substituent. The other Cr2+ ion bonds to an ipso carbon (Cr-C= ca. 2.53 Å) from its terphenyl substituent as well as four COT carbons (Cr--C= 2.24-2.32 Å). The COT carbon-carbon distances display an alternating pattern, consistent with the non-planarity and non-aromatic character of the ring. The magnetic properties of 6.1 indicate that the Cr2+ ions have a high-spin d4 configuration with S = 2. The temperature dependence of the magnetism indicates that their behavior is due to zero-field splitting of the S = 2 state. Attempts to prepare 6.1 by the direct reaction of quintuple-bonded (CrAriPr4)2 with COT were unsuccessful. (Abstract shortened by UMI.) --Proquest.
Author: Xue Duan
Publisher: Springer
ISBN: 9783540104940
Category : Science
Languages : en
Pages : 204
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Author: Bruce Averill
Publisher:
ISBN: 9780321413703
Category : Chemistry
Languages : en
Pages : 1233
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Emphasises on contemporary applications and an intuitive problem-solving approach that helps students discover the exciting potential of chemical science. This book incorporates fresh applications from the three major areas of modern research: materials, environmental chemistry, and biological science.
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: John L Burmeister
Publisher: World Scientific
ISBN: 9814488003
Category : Science
Languages : en
Pages : 654
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Book Description
This invaluable book distils the research accomplishments of Professor Fred Basolo during the five decades when he served as a world leader in the modern renaissance of inorganic chemistry. Its primary focus is on the very important area of chemistry known as coordination chemistry.Most of the elements in the periodic table are metals, and most of the chemistry of metals involves coordination chemistry. This is the case in the currently significant areas of research, including organometallic homogenous catalysis, biological reactions of metalloproteins, and even the solid state extended structures of new materials. In these systems, the metals are of primary importance because they are the sites of ligand substitution or redox reactions. In the solid materials, the coordination number of the metal and its stereochemistry are of major importance.Some fifty years of research on transition metal complexes carried out in the laboratory of Professor Basolo at Northwestern University is recorded here as selected scientific publications. The book is divided into three different major research areas, each dealing with some aspect of coordination chemistry. In each case, introductory remarks are presented which indicate what prompted the research projects and what the major accomplishments were. Although the research was of the academic, curiosity-driven type, some aspects have proven to be useful to others involved in projects that were much more applied in nature.
Author: Michael Isaac Lipschutz
Publisher:
ISBN:
Category :
Languages : en
Pages : 139
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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.
Author: Vahdat Jahed
Publisher:
ISBN:
Category : Borates
Languages : en
Pages : 0
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Book Description
In biological systems, O2 interaction with iron centers in enzyme structure occurs during respiration and the metabolic process. To fully understand the interaction mechanism, each step of the O2 reduction process is important and needs to be characterized. To this goal, we have synthesized and characterized a series of cationic five-coordinate iron complexes, [FeII(L)(L')]+ where L is TpMe, Me = hydrotris{3,5-dimethylpyrazol-1-yl}borate; TpPh, Me = hydrotris{3-phenyl-5-methylpyrazol-1-yl}borate; L'= 2,2'-bipyridine; 4,4'-dimethoxy-2,2'-bipyridine; 4,4'-dimethyl-2,2'-bipyridine; 4,4′-bis(trifluoromethyl)-2,2′-bipyridine; 4,4'-dibromo-2,2'-bipyridine. These complexes were utilized to activate O2 to isolate iron-oxygen intermediate species. The electronic spectra indicate intense absorption at 390 nm consisting of O2 binding to the mononuclear iron complex that generates an iron oxygen intermediate. In addition, the effect of the ligand on the stability of the potential intermediate was studied by altering the ligand substitute. We also treated the high-spin iron(II) reaction with CO to generate the corresponding adduct of low-spin iron(II). 1HNMR analysis reveals a diamagnetic complex arising from a spin-state change from S = 2 to S = 0. Furthermore, infrared spectroscopy has been used to support CO binding empirically. In chapter 3, my research studies nitrene chemistry. Nitrenes are chemically analogous to a single oxygen atom (i.e., NR vs. O). Therefore, nitrene can insert into other chemical bonds. Such reactivity can install synthetically valuable carbon-nitrogen bonds into hydrocarbon substrate. Affording shorter routes to high-value commodity chemicals. However, free nitrenes are generated with difficulty and often display rapid and unselective reactivity. Some degree of control can be achieved through the coordination of nitrene within the ligand field of a metal complex. Structural and electronic modifications affect nitrene reactivity and enable catalyst optimization by characterizing reactive intermediates. We provided a rare example of an octahedral high valent iron imido complex. In chapter 4, polydentate ligand systems have been used to synthesize a new series of late first-row transition metal complexes. We employed Tp hydrotris(pyrazolyl)borates and Bp hydrobis(pyrazolyl)borates to synthesize five-coordinate complexes, [(L)M(L')] where (L is TpPh, Me, TpMe, Me; L'= BpPh, Me, BpH, H; and M= Fe, Co, Ni) to investigate their coordination chemistry. Various sterically hindered ligand systems show an interesting effect on the ligand orientation in the complex structure.
Author: William John Rozell
Publisher:
ISBN:
Category : Complex compounds
Languages : en
Pages : 340
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Author: Mandeep Dalal
Publisher: Dalal Institute
ISBN: 8193872002
Category : Science
Languages : en
Pages : 480
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Book Description
An advanced-level textbook of inorganic chemistry for the graduate (B.Sc) and postgraduate (M.Sc) students of Indian and foreign universities. This book is a part of four volume series, entitled "A Textbook of Inorganic Chemistry – Volume I, II, III, IV". CONTENTS: Chapter 1. Stereochemistry and Bonding in Main Group Compounds: VSEPR theory, dπ -pπ bonds, Bent rule and energetic of hybridization. Chapter 2. Metal-Ligand Equilibria in Solution: Stepwise and overall formation constants and their interactions, Trends in stepwise constants, Factors affecting stability of metal complexes with reference to the nature of metal ion and ligand, Chelate effect and its thermodynamic origin, Determination of binary formation constants by pH-metry and spectrophotometry. Chapter 3. Reaction Mechanism of Transition Metal Complexes – I: Inert and labile complexes, Mechanisms for ligand replacement reactions, Formation of complexes from aquo ions, Ligand displacement reactions in octahedral complexes- acid hydrolysis, Base hydrolysis, Racemization of tris chelate complexes, Electrophilic attack on ligands. Chapter 4. Reaction Mechanism of Transition Metal Complexes – II: Mechanism of ligand displacement reactions in square planar complexes, The trans effect, Theories of trans effect, Mechanism of electron transfer reactions – types; Outer sphere electron transfer mechanism and inner sphere electron transfer mechanism, Electron exchange. Chapter 5. Isopoly and Heteropoly Acids and Salts: Isopoly and Heteropoly acids and salts of Mo and W: structures of isopoly and heteropoly anions. Chapter 6. Crystal Structures: Structures of some binary and ternary compounds such as fluorite, antifluorite, rutile, antirutile, crystobalite, layer lattices- CdI2, BiI3; ReO3, Mn2O3, corundum, pervoskite, Ilmenite and Calcite. Chapter 7. Metal-Ligand Bonding: Limitation of crystal field theory, Molecular orbital theory, octahedral, tetrahedral or square planar complexes, π-bonding and molecular orbital theory. Chapter 8. Electronic Spectra of Transition Metal Complexes: Spectroscopic ground states, Correlation and spin-orbit coupling in free ions for Ist series of transition metals, Orgel and Tanabe-Sugano diagrams for transition metal complexes (d1 – d9 states), Calculation of Dq, B and β parameters, Effect of distortion on the d-orbital energy levels, Structural evidence from electronic spectrum, John-Tellar effect, Spectrochemical and nephalauxetic series, Charge transfer spectra, Electronic spectra of molecular addition compounds. Chapter 9. Magantic Properties of Transition Metal Complexes: Elementary theory of magneto - chemistry, Guoy’s method for determination of magnetic susceptibility, Calculation of magnetic moments, Magnetic properties of free ions, Orbital contribution, effect of ligand-field, Application of magneto-chemistry in structure determination, Magnetic exchange coupling and spin state cross over. Chapter 10. Metal Clusters: Structure and bonding in higher boranes, Wade’s rules, Carboranes, Metal Carbonyl Clusters - Low Nuclearity Carbonyl Clusters, Total Electron Count (TEC). Chapter 11. Metal-π Complexes: Metal carbonyls, structure and bonding, Vibrational spectra of metal carbonyls for bonding and structure elucidation, Important reactions of metal carbonyls; Preparation, bonding, structure and important reactions of transition metal nitrosyl, dinitrogen and dioxygen complexes; Tertiary phosphine as ligand.
