Metal Mediated Template Synthesis Of Ligands

Metal Mediated Template Synthesis Of Ligands
Author: Costisor Otilia
Publisher: World Scientific
Total Pages: 307
Release: 2004-04-27
Genre: Science
ISBN: 9814482889

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This book surveys the relatively new area of the synthesis of organic ligands when metal ions act as a template. In the last fifty years this field has undergone an explosive development, marked by a great amount of literature. The material in the book has been arranged according to the type of chemical reaction involved. In this frame, the basic principles of metal template reactions and the shape of the molecules are considered. Designed to satisfy the demands of students, young researchers doing their PhDs, and those working in the field of coordination chemistry, the book details the role of the metal ions and the specific properties of the formed complexes.Metal Mediated Template Synthesis of Ligands offers a comprehensive analysis with wide-ranging references and provides an extensive overview of research on metal-directed organic ligands over the past five decades.

Direct Synthesis of Metal Complexes

Direct Synthesis of Metal Complexes
Author: B.I. Kharisov
Publisher: Elsevier
Total Pages: 470
Release: 2018-04-19
Genre: Science
ISBN: 0128110627

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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

Synthesis and Coordination Chemistry of Multidentate Ligands Based on Nitrogen-containing Heterocyclic Phenanthridine Moieties

Synthesis and Coordination Chemistry of Multidentate Ligands Based on Nitrogen-containing Heterocyclic Phenanthridine Moieties
Author: Rajarshi Mondal
Publisher:
Total Pages: 0
Release: 2020
Genre:
ISBN:

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This project explored the synthesis of bi-functional neutral donor ligands using pi-extended phenanthridine system which can stabilize the late transition metals. My interest would be the phenanthridine ring of 14 pi-electron polycyclic heteroaromatic system, which is the building block of my ligands and the properties of this extended aromatic system while binding with late transition metals and comparing with smaller congener quinoline precursor for understanding the effect of site dependent pi extension. The application and properties of designed metal complexes have been extensively studied. The study of using pi-extended phenanthridine as a ligand and its metal complexes would open a new window of opportunities. A synthetic route to bromo functionalization of benzo-fused N-heterocyclic phenanthridine, enabling the constructions of both phosphinophenanthridine and NHC carbene-phenanthridine have been devised, which are heterobifunctional Lewis base containing both phosphine/carbene and phenanthridine donors. The coordination chemistry for both phosphine/carbene ligands with ions of late first-row transition metals has been explored. 4-Bromophenanthridine was synthesized by Suzuki cross-coupling/condensation, 6-substitution was conducted by reaction between phenanthridinone and phosphine(V) oxyhalide. The installation of phosphine was directed by lithium-halogen exchange of 4-bromophenanthridine. The carbenes were placed by the reaction between 6-halophenanthridine and corresponding imidazole in high temperature. A series of halide bridge Cu complexes were synthesized using phosphino-phenanthridine ligand to check the effect of site selective pi-extension on emission property by comparing with smaller congener quinoline based Cu complexes. Further study leads to design of sterically encumbered phenanthridine for diminishing the excited state geometric orientation. A relative effect of counterion in solid-state emission lifetime has also been studied. A group of octahedral d8 metal complexes were synthesized by using both phosphine/carbene ligands to study the metal to ligand charge transfer and its lifetime. The potential of these complexes for use in the field of photosensitizer was also discussed. Phosphino ligand based Fe complexes have been synthesized and their use in the filed of hydrogenation catalysis has also been discussed.

Direct Synthesis of Coordination and Organometallic Compounds

Direct Synthesis of Coordination and Organometallic Compounds
Author: A.D. Garnovskii
Publisher: Elsevier
Total Pages: 255
Release: 1999-08-13
Genre: Science
ISBN: 0080530443

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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).

Multidentate Phosphino-alkene Ligands and Their Late Transition Metal Complexes

Multidentate Phosphino-alkene Ligands and Their Late Transition Metal Complexes
Author: Amanda G. Jarvis
Publisher:
Total Pages:
Release: 2011
Genre:
ISBN:

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The synthesis and characterisation of a new class of multidentate conformationally flexible phosphino-alkene ligands, called dbaPHOS (127) and monodbaPHOS (128), are described is this PhD thesis. The related phosphine sulphide ligands, namely dbaTHIOPHOS (137) and monodbaTHIOPHOS (149), have also been prepared. The coordination chemistry of the novel ligands was investigated with a variety of late-transition metals, including Cu, Rh, Pd and Pt. X-ray crystal structure determination of the complexes containing these ligands highlights the multiple coordination modes and versatility of each ligand system. The ability of the 1,4-dien-3-one backbone to adopt different conformational geometries around metal centers is of particular note. DbaPHOS (127) was found to act as a cis- and trans-chelating bisphosphine in both square planar PdII and PtII complexes. The 1,4-dien-3-one motif is hemilabile; exchange between coordinated and non-coordinated alkenes is observed in both the Pd0 complex, 167, and the related cationic CuI complex, 193. An investigation into the CuI complexes' activity in the cyclopropanation of styrene, as catalysts, showed that they are commensurate with other recently reported systems. In addition to the coordination chemistry of the novel ligand systems, some interesting findings emerged in the ligand synthesis and characterisation studies. For example, monodbaTHIOPHOS (149) undergoes an interesting solid-state [2+2] intramolecular cycloaddition transformation, giving cycloadduct, 206. Furthermore, 2-hydroperoxytetrahydrofuran was found to be an impurity in the microwave-assisted Horner-Wadsworth-Emmons reaction of 2-(diphenylthiophosphine)benzaldehyde (136) with 1,3-bis-(ethoxyphosphonato)-acetone (130) to give of dbaTHIOPHOS (137) and an unexpected THF insertion product, 138. The latter is explained by a side reaction involving the reduced compound, tetrahydrofuran-2-ol, derived from 2-hydroperoxytetrahydrofuran.