Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands


Book Description

This book explores the development of the first open-shell heavier tetrylidyne complexes featuring a tetrel-centered unpaired electron, and unprecedented metallatetrylidynes containing a multiply-bonded, linear-coordinated single heavier tetrel atom embedded between two metal centers. The chemistry of compounds featuring triple bonds of the heavier Group-14 elements Si–Pb with transition metals is a very challenging research area, which combines modern molecular main-group element with transition-metal chemistry, and is of fundamental importance for the understanding of chemical bonding. During the last 15 years, the research in this area has witnessed considerable progress in isolating a series of closed-shell tetrylidyne complexes. However, despite numerous attempts, open-shell tetrylidyne complexes and heavier group 14 element congeners of metallacarbynes and carbide complexes remained inaccessible. In this book, readers will find more about the reactivity studies of these novel complexes that uncovered a plethora of exceptional products, including a novel m3-silicido complex, the first dimetallasilacumulene with a linear, two-coordinated single silicon atom and the first compounds of planar tetracoordinated silicon (ptSi) (Anti-van’t Hoff-Le Bell Silicon). Readers will also learn about the isolation and full characterization of the first room-temperature stable disilavinylidene, a silicon analogue of the very reactive vinylidenes (R2C=C:), and the first intermetallic plumbylidyne ligand transfer reactions.




Activated Metals in Organic Synthesis


Book Description

Activated Metals in Organic Synthesis discusses fundamental principles of the generation of activated, highly reactive metals, and their applications in organic synthesis. Following an introductory chapter on basic forms of metals the chapters in Part 1 are devoted to common strategies utilized for the preparation of active metals. These strategies include vaporization and subsequent co-condensation of metal atoms, in addition to depassivating methods employed commonly in laboratory syntheses. Chapters in Part 2 discuss relevant organic transformations in which metal activation plays a crucial role. Specific topics covered include metal-induced reductive methods; pinacolic, Reformatsky-, and Barbier-type reactions; McMurry ketone-olefin coupling; and the Bernet-Vasella reaction. Each chapter is followed by literature citations ranging from specific references to significant reviews. Many structural formulas are provided, making it easy to follow each synthesis. The book will be an important reference for students, organic chemists, and researchers in all areas of organometallic chemistry.







Transition Metals in Organic Synthesis


Book Description

This volume is designed to disseminate practical expertise in this important and demanding area of chemistry to undergraduate and postgraduate students in universities and to researchers working in the chemical industry. The authors have considerable practical and teaching experience in theareas they cover. Topics include transition metal-promoted oxidations, palladium-catalysed carbon-carbon bond formation, ferrocene chemistry, applications of organoiron complexes in organic synthesis, applications of titanocene and zirconocene complexes in organic synthesis and arene chromiumtricarbonyl chemistry.




Transition Metals in the Synthesis of Complex Organic Molecules


Book Description

The third edition of Transition Metals in the Synthesis of Complex Organic Molecules is a comprehensive revision and significant expansion of the second edition. The clear and systematic approach to the formation, manipulation, and reactivity of organometallic complexes has been maintained. The book is divided into 10 chapters starting with general formalisms, electron counting, and basic principles of organometallic reaction mechanisms. The organic chemistry of transition metals is then presented by class of metal complex, with many examples of applications in the synthesis of complex natural products and pharmaceuticals. The book is ideal for advanced undergraduate and graduate students as well as all practicing synthetic organic chemists. It is written for organic chemists and offers an easy entry into the field of organotransition metal chemistry without requiring a background in inorganic chemistry.







Synthesis, Characterization, and Reactivity Evaluation of Late Transition Metal-Aluminum Heterobimetallic Complexes Toward Molecular Hydrogen


Book Description

The investigation and development of heterobimetallic systems has seen a meteoric surge over the past decade. Generally, these heterobimetallic systems involve two transition metals with distinct properties used together to activate chemical bonds. Many heterobimetallics consist of a soft, low-valent metal and a harder, high-valent metal. The unique electronics afforded by heterobimetallics of this sort can be exploited, yielding access to novel reactivities that may be otherwise inaccessible to a single transition metal. Less studied are heterobimetallic complexes composed of one late transition metal (LTM) and one Lewis-acidic p-block (Group 13) metal. Due to its electropositivity being the highest among Group 13 metals as well as its high earth-abundance, aluminum holds particular interest to the Brewster laboratory. In contrast to their exhaustively investigated boron analogues, the field of aluminum-containing heterobimetallics is relatively uncultivated due to the high reactivity and synthetic difficulty of aluminum species, making isolation and characterization quite challenging. One of the aims of the Brewster lab is to develop heterobimetallic systems comprised of an electron-rich, low-valent transition metal and aluminum to investigate potential synergistic reactivity between both metal centers. In this dissertation, I report the successful synthesis and electronic characterization of myriad novel mono- and heterobimetallic complexes of either iridium or rhodium and aluminumover 35 new complexes in total. Moreover, I detail the ability of selected heterobimetallic complexes to facilitate activation of molecular hydrogen as well as hydrogenolysis, thereby generating alkane gas..







The Zintl Chemistry of the Heavy Tetrel Elements


Book Description

Exploration of the alkali metal/alkaline-earth metal/heavy tetrel (Sn or Pb) systems has revealed a vast array of new chemistry and novel structure types. The structures and properties of these new materials have been studied in an attempt to understand the chemistry of these and other related systems. The first phase reported is Rb4Pb9 (K4Pb9 type). The compound contains two different types of Pb94− deltahedra, a monocapped square pyramid and a distorted tricapped trigonal prism. Both cluster geometries correspond to a nido assignment even though the tricapped trigonal prism is not the classic Wade's rules nido deltahedron expected for a monocapped square antiprism. Also, a series of compounds that contain square pyramidal Tt5 polyanions of tin and lead has been obtained in alkaline-earth or rare-earth metal-tetrel systems by direct fusion of the elements to yield Sr3Sn5, Ba3Pb5, and La3Sn5. These phases contain square pyramidal clusters of the tetrel elements that are weakly interlinked into chains via two types of longer intercluster interactions that are mediated by bridging cations and substantially influenced by cation size and the free electron count. Attempts at incorporating another main-group element to form heteroatomic clusters were also successful. In the case of A5InPb (A = K, Rb), the compounds contain clusters composed of two Pb4 tetrahedra that are interbridged by a lone [mu]6-In atom. The InPb units are weakly interlinked into sheets in the ab plane by long intercluster Pb-Pb interactions. Using As led to the formation of the compound K5As3Pb3 which is made up of As3Pb35− crown clusters that can be likened to a 6-atom hypho-cluster based on the tricapped trigonal parent as the closo structure. These crowns are connected via intercluster bonds to form infinite chains down the b axis. This work also reports on a disordered phase Na23In{sub 40.4(1)}Pd{sub 2.51(2)}. The major structural features include a 12-bonded-closo-In12 icosahedron, a 15-bonded-closo-In15 cluster, and an 18-bonded-21-atom spacer.