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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.
This outstanding thesis describes a detailed investigation into the use of low-oxidation-state group 14 complexes in catalysis, developed at the cutting edge of inorganic and organometallic chemistry. It includes the preparation of a number of landmark compounds, some of which challenge our current understanding of metal–metal bonding and low-oxidation-state main group chemistry. Among the many highlights of this thesis, the standout result is the development of the first well-defined, low- oxidation-state main group hydride systems as highly efficient catalysts in the hydroboration of carbonyl substrates, including carbon dioxide, which are as efficient as those observed in more traditional, transition-metal catalyses. These results essentially define a new subdiscipline of chemistry.
T. Ziegler: A Chronicle About the Development of Electronic Structure Theories for Transition Metal Complexes.- J. Linderberg: Orbital Models and Electronic Structure Theory.- J.S. and J.E. Avery: Sturmians and Generalized Sturmians in Quantum Theory.- B.T Sutcliffe: Chemistry as a “Manifestation of Quantum Phenomena” and the Born–Oppenheimer Approximation?- A.J. McCaffery: From Ligand Field Theory to Molecular Collision Dynamics: A Common Thread of Angular Momentum.- M. Atanasov, D. Ganyushin, K. Sivalingam and F. Neese: A Modern First-Principles View on Ligand Field Theory Through the Eyes of Correlated Multireference Wavefunctions.- R.S. Berry and B.M. Smirnov: The Phase Rule: Beyond Myopia to Understanding.
Early Main Group Metal Catalysis gives a comprehensive overview of catalytic reactions in the presence of group 1 and group 2 metals. Chapters are ordered to reaction type, contain educational elements and deal with concepts illustrated by examples that cover the main developments. After a short introduction on polar organometallic chemistry and synthesis of early main group metal complexes, a variety of catalytic reactions are described, e.g. polymerization of alkenes, hydroamination and phosphination reactions, hydrosilylation, hydroboration and hydrogenation catalysis, as well as enantioselective and Lewis-acid catalysis. The book addresses organic chemists and researchers in industry interested in the state-of-the-art and new possibilities of early main group metal catalysis as well as newcomers to the field. Written by a team of leaders in the field, it is a very welcome addition to the area of main group metal chemistry, and to the field of catalysis.
The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics of pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors. All chapters from Topics in Organometallic Chemistry are published OnlineFirst with an individual DOI. In references, Topics in Organometallic Chemistry is abbreviated as Top Organomet Chem and cited as a journal
The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics in pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors.