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

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 synthesis, full characterization and 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. Front Matter ....Pages i-xxii Introduction (Priyabrata Ghana)....Pages 1-15 Front Matter ....Pages 17-17 Closed Shell Heavier Tetrylidyne Complexes of Group 6 Metals (Priyabrata Ghana)....Pages 19-75 Open-Shell Heavier Tetrylidyne Complexes of Group 6 Transition Metals (Priyabrata Ghana)....Pages 77-81 Germylidyne Mediated C–C Coupling Reaction of Isonitriles—Formation of an N-Heterocyclic Germylene (Priyabrata Ghana)....Pages 83-86 A New Method for the Synthesis of Manganese Tetrylidyne Complexes (Priyabrata Ghana)....Pages 87-102 An Open-Shell Manganese Stannylidyne Comprising of a Tin-Centered Unpaired Electron (Priyabrata Ghana)....Pages 103-113 μ-Ylido Complexes (Priyabrata Ghana)....Pages 115-128 Chemistry of the Metallatetrylidyne Complexes (Priyabrata Ghana)....Pages 129-163 Plumbylidyne Transfer Reaction (Priyabrata Ghana)....Pages 165-178 Access to the First NHC-Stabilized Disilavinylidene (Priyabrata Ghana)....Pages 179-191 Front Matter ....Pages 193-193 Summary (Priyabrata Ghana)....Pages 195-202 Outlook (Priyabrata Ghana)....Pages 203-205 Experimental Section (Priyabrata Ghana)....Pages 207-297 Back Matter ....Pages 299-344