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The results obtained from DFT calculations not only gave a good support to the experimental results and verified the experimentally demonstrated Ni-atom transfer mechanism from Ni=E (E = CH2, NH, PH) activating complex to ethylene to form three-membered ring products but also validated the application of late transition metal complexes in respective process.
This book focuses on the electronic properties of transition metals in coordination environments. These properties are responsible for the unique and intricate activity of transition metal sites in bio- and inorganic catalysis, but also pose challenges for both theoretical and experimental studies. Written by an international group of recognized experts, the book reviews recent advances in computational modeling and discusses their interplay using experiments. It covers a broad range of topics, including advanced computational methods for transition metal systems; spectroscopic, electrochemical and catalytic properties of transition metals in coordination environments; metalloenzymes and biomimetic compounds; and spin-related phenomena. As such, the book offers an invaluable resource for all researchers and postgraduate students interested in both fundamental and application-oriented research in the field of transition metal systems.
The role of bulky tin ligands in the stabilization of transition metal complexes with electronic unsaturation has been studied to understand the mode of binding of small molecules at an unsaturated metal center. We were able to isolate electronically unsaturated Pt-Sn bimetallic complexes effective in the reversible activation of small molecules including CO, H2, C2H4, and NH3 at room temperature. We have examined the effect of the modification of ligands in Pt-Sn bimetallic complexes for the activation of small molecules and have observed that the Pt(SnBut3)2(CNBut)2 bimetallic complex reversibly activates hydrogen at room temperature both in the solid state and in solution. Similarly, we have also prepared bimetallic Pt-Sn complexes with an NHC carbine ligand which were also shown to activate hydrogen and alkenes reversibly. A bimetallic Fe-Sn cluster complex, Fe2 ([mu]-SnBut2)2(CO)8, was synthesized from the reaction of But3SnH with the Fe2(CO)9 and shown to be selective at activating the benzylic C-H bond of alkylaromatic solvent molecules. The new complexes containing tin have been characterized spectroscopically to gain an insight into the reaction mechanism involved in small molecule activation.
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.
This second edition offers easy access to the field of organotransition metal chemistry. The book covers the basics of transition metal chemistry, giving a practical introduction to organotransition reaction mechanisms.