Download Advances in Organometallic Chemistry, Vol. 48 by Robert West, Anthony F. Hill PDF

By Robert West, Anthony F. Hill

ISBN-10: 0120311488

ISBN-13: 9780120311484

Just about all branches of chemistry and fabric technological know-how now interface with organometallic chemistry-the research of compounds containing carbon-metal bonds. Organometallic compounds diversity from species that are so reactive that they just have a brief life at ambient temperatures to species that are thermally very reliable. This largely acclaimed serial includes authoritative experiences that tackle all facets of organometallic chemistry, a box which has increased significantly because the ebook of quantity 1 in 1964.

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This in situ formation of an NHC–metal complex can be achieved by the addition of an excess of a base, which is typically present as a stoichiometric reagent in most of the Heck-type reactions. The use of such in situ systems consisting of imidazolium salts and palladium(0) or palladium(II) precursors has proven highly efficient for the Suzuki–Miyaura reaction,341,342 the Kumada–Corriu reaction,41 the cross-coupling of phenyltrimethoxysilane,343 and the Buchwald– Hartwig amination,344 even enabling the conversion of aryl chlorides (using 65 and 66).

Generally accepted representations of the metal–carbon bond of metal coordinated NHCs. 269 In summary, the metal– carbon bond of an NHC is significantly different from a “real” metal– carbene bond both of the Fischer- or Schrock-type. Thus, the representations of the metal–carbon bond according to Scheme 9 is now generally accepted. As a result, the reactivity of these metal–NHC compounds is also unique. They prove to be rather resistant toward attack by nucleophiles or electrophiles at the divalent carbon atom.

NHCs are certainly not the best choice for requirement (ii), but seem to be superior with respect to (i). This has been quantified by theoretical calculations: The dissociation energies of NHCs and phosphines for ruthenium alkylidene model compounds by density functional (DFT) methods according to Eq. 159 TABLE IV CALCULATED LIGAND DISSOCIATION ENERGIES E [kcal mol−1] FOR a THE MODEL COMPOUNDS ACCORDING TO Eq. (41). 4) a Ligand dissociation energies without ethylene coordination are given in parentheses.

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