The metal-carbon bonds in metal carbonyls have both σ and n characters. A σ bond isformed when the carbonyl carbon donates a lone pair of electrons to the vacant orbital ofthe metal. A n bond is formed by the donation of a pair of electrons from the filled metald orbital into the ...
The Nature of the Transition Metal-Carbonyl Bond and the Question About the Valence Orbitals of Transition Metals. A Bond-Energy Decomposition Analysis of TM(CO)6q (TMq = Hf2‑, Ta-, W, Re+, Os2+, Ir3+). J. Am. Chem. Soc. 2000, 122, 6449-6458....
of new cross-coupling reactions that use catalysts based on inexpensive and non-toxic metals is attracting increasing attention. Similarly, efficient processes that do not require a metal catalyst are of extraordinary interest. Here, we report a new and efficient metal-free carbon–carbon bond-...
enzymes functionalize diverse substrates containing benzylic, allylic or α-amino C–H bonds with high turnover and excellent selectivity. Furthermore, they have enabled the development of concise routes to several natural products. The use of the native iron-haem cofactor of these enzymes to mediate...
Unlike metal chemocatalysis, enzymes can catalyse C−H bond functionalization, discriminating between near-identical, non-activated C−H bonds, delivering products with exquisite regioselectivity. However, enzymes typically provide access to fewer functionalities than more divergent chemocatalysis. Here we...
Natural abundance 13C kinetic isotope effects provide quantitative information about the transition-state structures of two key elementary steps in the catalytic cycle, transmetallation and oxidative addition. Experiments with configurationally stable, deuterium-labelled substrates revealed that oxidative ...
Human papillomavirus (HPV) is a significant contributor to the global cancer burden, and its carcinogenic activity is facilitated in part by the HPV early protein 6 (E6), which interacts with the E3-ligase E6AP, also known as UBE3A, to promote degradatio
we sought to create scaffolds that could provide β-strand pairing interactions to all the backbone amide and carbonyl atoms of the peptide, such that the peptide strand complements a β-sheet on the scaffold (Fig.1). Starting from FoldIt designed proteins with mixed α/β topology29, we des...
metal–ligand bindingWhen carbonyl ligands coordinate to transition metals, their bond distance either increases (classical) or decreases (nonclassical) with respect to the bond length in the isolated CO molecule. C–O expansion can easily be understood by p ‐backヾonation, which results in a ...
Transition metal-carbon complexes. A theoretical study The metal-carbon bonds in the 18VE complexes 2Ru-3Fe are weaker than those in the 16VE species. Calculations of the related carbonyl complexes [(PMe... A Krapp,KK Pandey,G Frenking - 《Journal of the American Chemical Society》 被引量...