Despite a tremendous number of books, monographs, textbooks and review-articles devoted to “organometallic chemistry”, the largest part of those contributions have been designed into following structure of the content: (i) Manuals, handbooks and encyclopedias summarizing important organometallic reagents in the organic synthesis; (ii) Books, containing synthetic protocols for obtaining of organometallic reagents; and (iii) Manuals on basic organic reactions catalysed by organometallics.
However, there are scarce efforts devoted to studies of reaction mechanisms, physical and chemical properties and structure of organometallics. Furthermore the largest part of available literature has been organized to serve educational needs of undergraduate and graduate students at different areas of chemist including inorganic, organic and/or physical chemistry, so that it has textbook (or a mixing) style, rather than to represent monographs on advances in organometallic research.
In this context, our book firstly in the literature has treated experimental and theoretical contributions in understanding reaction mechanisms, involving organosilver reagents as well as molecular structure and physical properties, focusing attention on chemical aspects of nature of C–M bond and role of coordination environment of inner coordination sphere of metal ion to effectiveness of mediated organic reactions from a coordination chemistry point of view, rather than to review available chemical reactions. Thus highlighting the main goal of this book to serve as a useful source of information about those molecular factors and properties governing the usefulness of those chemical classes to organic synthesis, which is important for further molecular design of new intermediates having enhanced synthetic efficiency, high enantioselectivity at mild experimental conditions.
Table of Contents
I. Summary
II. Introduction
III. Mononuclear organometallics
IV. Dinuclear organometallics
V. Polynuclear organometallics
VI. π–Complexes
VII. Conclusion and outlook
Appendix A: Multi–isotopic modelling of mass spectra
Appendix B
Appendix C: Ab initio effective core potentials
Objectives and Topics
This book aims to provide a comprehensive understanding of the molecular factors and properties governing the effectiveness of organosilver reagents in organic synthesis, bridging experimental data with theoretical insights from coordination chemistry. It focuses on characterizing the nature of metal–ligand bonds and reaction mechanisms to facilitate the design of more efficient and selective organometallic catalysts.
- Correlation between molecular structure and chemical reactivity of organosilver compounds.
- Advanced applications of mass spectrometry and X-ray diffraction in structural elucidation.
- Theoretical modeling of kinetic and thermodynamic properties using quantum chemistry.
- Mechanistic insights into catalytic decarboxylation, C–H activation, and C–C bond formation.
- Development of robust mediating compounds for laboratory and industrial applications.
Excerpt from the Book
MONONUCLEAR ORGANOMETALLICS
From a coordination chemistry point of view the largest class of organosilver intermediates which has received increasing attention over decades enormous efforts in development of the organosilver mediated organic synthetic reactions are mononuclear complexes of AgI/II–ions. They have found application to many organometallic catalysing processes starting this part of he chapter with the reactions of decarboxylation, which have significant importance in the field of the organic chemistry [19,20]. Despite, fact that reactions of decarboxylation can yielded to organometallics, in general, the process not always produce organometallic intermediates [3–10]. To a further understanding of the elementary step of this reaction method of mass spectrometry employed in numerous studies has yielded to important information, regarding the kinetic of the process and the molecular rearrangement at the transition state resulting to formation of the Ag–C bond via breaking of C–C(OOH) bond of corresponding carboxylic acid [3,4,6]. There are found that decarboxylation process is associated with the lowest energy pathway involving decomposition of the organic acid via decarboxylation as well as the elimination of the carboxylate anion and the auxiliary ligand (chemical processes (1)–(3)).
Summary of Chapters
I. Summary: Provides an overview of the book’s focus on correlating the molecular structure of silver-containing organometallics with their chemical properties to guide future reagent design.
II. Introduction: Discusses the significance of organosilver reagents in organic synthesis and outlines the methodological reliance on mass spectrometry and X-ray diffraction for structural analysis.
III. Mononuclear organometallics: Details the coordination chemistry and reaction mechanisms of mononuclear silver complexes, specifically focusing on decarboxylation and C-H activation.
IV. Dinuclear organometallics: Examines the role of dinuclear organometallic cluster cations in C-C and C-H bond activation processes and their associated fragmentation pathways.
V. Polynuclear organometallics: Explores the formation and mechanistic aspects of silver-alkynyl clusters and polynuclear complexes, emphasizing their utility in complex catalytic transformations.
VI. π–Complexes: Focuses on the bonding models, such as the Dewar–Chatt–Duncanson model, for silver(I)-arene and silver(I)-ethene π-interactions.
VII. Conclusion and outlook: Summarizes the integration of experimental and theoretical approaches to advance the design of new organometallic complexes in interdisciplinary sciences.
Keywords
Organosilver intermediates, Mass spectrometry, Quantum chemistry, Single crystal X–ray diffraction, Organic synthesis, Materials research, Coordination chemistry, Catalysis, Reaction mechanisms, Bond dissociation energy, Molecular structure, Ligand design, Chemical reactivity, Thermodynamics, Kinetics.
Frequently Asked Questions
What is the primary focus of this work?
The book focuses on the coordination chemistry of silver-containing organometallics, providing a deep dive into the molecular structure and properties that make these compounds effective mediators in organic synthesis.
What are the main thematic areas covered?
Key areas include organosilver reaction mechanisms (such as decarboxylation and bond activation), mass spectrometric characterization, quantum chemical modeling, and the structural study of π-complexes and clusters.
What is the main research objective?
The goal is to provide a comprehensive information source that correlates the molecular structure of organosilver compounds with their reactivity, thereby assisting in the design of highly efficient, enantioselective catalysts.
Which scientific methods are primarily utilized?
The research relies on a combination of experimental techniques, specifically single crystal X-ray diffraction and mass spectrometry, complemented by quantum chemical calculations to interpret experimental findings.
What topics are discussed in the main body?
The chapters cover mononuclear, dinuclear, and polynuclear organometallics, as well as π-complexes, with dedicated sections on theoretical approaches and structural determination.
Which keywords characterize the work?
The work is defined by terms like organosilver intermediates, mass spectrometry, quantum chemistry, organic synthesis, coordination chemistry, and materials research.
Why is mass spectrometry emphasized for these compounds?
Mass spectrometry is highlighted for its ability to provide structural information at attomol concentration ranges and to elucidate kinetic and thermodynamic data that are otherwise difficult to obtain.
What role do relativistic effects play in the theoretical calculations?
Relativistic effects are considered essential when working with heavy transition metal atoms (Z > 36) to accurately predict bond energies and orbital energies, which the book addresses through effective core potentials.
How is the Dewar–Chatt–Duncanson model applied?
It is used to explain the bonding in silver(I)-ethene and silver(I)-arene π-complexes, accounting for ligand-to-metal σ-donation and back-donation from the silver d-orbitals.
What is the significance of the decarboxylation study?
Decarboxylation reactions are used as a model system to understand the elementary steps of organosilver catalysis and the formation of key Ag–C bonds in gas-phase and condensed-phase chemistry.
- Quote paper
- Prof. Dr. Bojidarka Ivanova (Author), Michael Spiteller (Author), 2011, Molecular structure and properties of silver (I/II/III) containing organometallics, Munich, GRIN Verlag, https://www.grin.com/document/305751
