Odd electron organotransition metal complexes, once viewed as isolated exceptions to the 18-electron rule, are now recognized as a subset of compounds with unique reactivities. The identification of organometallic radicals as intermediates in the reaction mechanisms of even electron systems makes them increasingly important to the non-radical chemist as well. This book focuses on the generation, spectroscopic properties, structures, and reaction mechanisms exhibited by 17- and 19-electron organometallic complexes. The topics discussed center on transition metal complexes, although analogies to the chemistry of main group radicals are illustrated when appropriate. The material has been organized into ten self-contained chapters so that the reader can learn selectively about a particular area of interest. Two chapters focus on the techniques of electrochemistry and ESR spectroscopy, which are particularly suited to the study of organometallic radicals. Another chapter provides an overview of geometrical structrures for stable radicals.

Elementary radical reactions are described in terms of fundamental knowledge of organic chemistry and chemical physics in this valuable reference text. The complex radical processes of nonchain and chain mechanisms, such as dimerization, alkylation, polymerization, telomerization, halogenation pyrolysis, oxidation and combustion, are complemented by reactions in chemical lasers and in the cosmos, as well as by reactions in biological objects under normal or pathological metabolism. The text also provides the synthesis of facts from various fields of research and involves mechanisms where free radicals appear either as main or side intermediates in one of the several alternatives of the reaction pathway. Highlights include 38 tables and 39 figures.

Redox-Active Ligands Authoritative resource showcasing a new family of ligands that can lead to better catalysts and promising applications in organic synthesis Redox-Active Ligands gives a comprehensive overview of the unique features of redox-active ligands, describing their structure and synthesis, the characterization of their coordination complexes, and important applications in homogeneous catalysis. The work reflects the diversity of the subject by including ongoing research spanning coordination chemistry, organometallic chemistry, bioinspired catalysis, proton and electron transfer, and the ability of such ligands to interact with early and late transition metals, lanthanides, and actinides. The book is divided into three parts, devoted to introduction and concepts, applications, and case studies. After the introduction on key concepts related to the field, and the different types of ligands and complexes in which ligand-centered redox activity is commonly observed, mechanistic and computational studies are described. The second part focuses on catalytic applications of redox-active complexes, including examples from radical transformations, coordination chemistry and organic synthesis. Finally, case studies of redox-active guanidine ligands, and of lanthanides and actinides are presented. Other specific sample topics covered include: An overview of the electronic features of redox-active ligands, covering their historical perspective and biological background The versatility and mode of action of redox-active ligands, which sets them apart from more classic and tunable ligands such as phosphines or N-heterocyclic carbenes Preparation and catalytic applications of complexes of stable N-aryl radicals Metal complexes with redox-active ligands in H+/e- transfer transformations By providing up-to-date information on important concepts and applications, Redox-Active Ligands is an essential reading for researchers working in organometallic and coordination chemistry, catalysis, organic synthesis, and (bio)inorganic chemistry, as well as newcomers to the field.