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Direct Synthesis of Metal Complexes provides in-depth coverage of the direct synthesis of coordination and organometallic compounds. The work is primarily organized by methods, but also covers highly relevant complexes, such as metal-polymer coordination compounds. This updated reference discusses recent developments in cryosynthesis, electrosynthesis, and tribosynthesis (popular as it doesn’t require organic solvents), with special attention paid to ‘greener’ methodologies and approaches. Additionally, the book describes physical methods of zero-valent metal interaction with organic matter, including sputtering, ultrasonic treatment and synthesis in ionic liquids. The book presents completely new content as a follow-up to the 1999 Elsevier Science publication Direct Synthesis of Coordination and Organometallic Compounds that was edited by Dr. Garnovskii and Dr. Kharisov. Covers current methods and techniques of metal interactions with organic media leading to metal chelates, adducts, di- and polymetallic complexes, metal-containing macrocycles, supported coordination compounds (i.e., metal complexes on carbon nanotubes), and more Describes reactivities of distinct forms of elemental metals (powders, sheets, nanoparticles (including a host of less-common metal nanostructures) with organic phase (liquid, solid and gaseous) and water Includes experimental procedures, with examples of direct synthesis, at the end of each chapter
The first chiral amidinate borohydride rare earth compounds and compounds based on (S)-HPEBA ((S,S)-N,N-bis-(1-phenylethyl)benzamidine) ligand were reported by Roesky et al. To continuing this work, the new chiral ligand (S)-HNEBA ((S,S)-N,N-bis-(1-naphthylethyl)benzamidine) were synthesized. The corresponding amidinate metal complexes were successfully obtained by amine elimination. The luminescent and magnetic properties of rare earth compounds were studied. Alkaline earth metal compounds have been extensively studied as catalysts in synthetic chemistry. However, chiral amidinate alkaline earth metal complexes have never been reported. Chiral amidinate ligand (S)-HPEBA was introduced into the coordination chemistry of the alkaline earth metal as well as divalent lanthanides, their catalytic activities in hydrophosphination have been investigated. The Ba compound showed high catalytic activities in the hydrophosphination reaction. Moreover, since rare earth metal COT complexes exhibit excellent SMM behavior, it is of great interest to study the magnetic behavior of COT amidinate complexes. Thus, amidine ligand (S)-HPEBA and (S)-HPETA are introduced into the corresponding COT amidinate complexes for magnetic properties studies. The Er Compound exhibited typical field-induced SMM behavior. Furthermore, inspired by the promising application of lanthanide SMMs and the research of SMMs based on sandwich type lanthanide complexes, a series of novel sandwich type complexes comprising of Pc and COT ligand were designed and synthesized.
This book is devoted to the interaction between elemental metals and (in)organic ligands in different reaction conditions. Metals could be activated for further reactions as cryosynthesis, electrosynthesis and tribosynthesis, some of them with or without ultrasonic and microwave treatment. The kinetics of metal dissolution in various non-aqueous media is discussed in detail. Many methods are used nowadays to synthesize coordination compounds. Metal complexes are obtained mainly by the direct interaction of the components (the ligands and a source of the complex-forming metal), as a result of ligand and metal exchange, and under the conditions of template synthesis, which also include the method of nascent reagents. In these methods the source of the metal is either its salts or carbonyls. At the same time, it has long been known that coordination compounds may be obtained as a result of direct synthesis from zero-valent metals. Methods for the synthesis of complex compounds under the conditions of gas-phase reactions, oxidative dissolution of zero-valent metals in non-aqueous media, and in the solid phase have been developed. These methods have become the basis of a new field in synthetic chemistry - the direct synthesis of coordination and organometallic compounds from zero-valent metals. Particular aspects of the above problem have been described in a series of reviews and monographs. However, on the whole these main parts of the direct synthesis of metal complexes has not been dealt with in the review and monograph publications on coordination chemistry. So, the main objective of this book is to analyze, discuss and generalize the existing information in the area of direct reactions leading to the coordination and organometallic reactions. Some methods of direct synthesis have been developed in the former USSR (in particular, a lot of works on cryosynthesis, pioneered (1972-1973) and recent works on electrosynthesis) but, in spite of their novelty and/or wide applicability, they are practically unknown elsewhere due to the language barrier. Thus, another objective of this book is to acquaint the readers with the mentioned achievements. Every chapter contains the tables which describe all the reported data on direct reaction between metal atoms, metal particles or bulk metals with (in)organic ligans. There are some illustrations also (for example, the scheme of the reactor for gas-phase reaction between metal small particles and &bgr;-diketones).
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