By Robert West, Anthony F. Hill
Just about all branches of chemistry and fabric technological know-how now interface with organometallic chemistry-the examine of compounds containing carbon-metal bonds. Organometallic compounds diversity from species that are so reactive that they just have a brief lifestyles at ambient temperatures to species that are thermally very sturdy. This broadly acclaimed serial includes authoritative reports that tackle all features of organometallic chemistry, a box which has extended vastly because the book of quantity 1 in 1964.
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Extra resources for Advances in Organometallic Chemistry, Vol. 48
R N R R N R N R N + N R N N N N (49) 2 N R R N R N R R R 1. Hydrosilylation Rhodium(I) and ruthenium(II) complexes containing NHCs have been applied in hydrosilylation reactions with alkenes, alkynes, and ketones. Rhodium(I) complexes with imidazolidin-2-ylidene ligands such as [RhCl(η4-cod)(NHC)], [RhCl(PPh3)2(NHC)], and [RhCl(CO)(PPh3)(NHC)] have been reported to lead to highly selective anti-Markovnikov addition of silanes to terminal oleﬁns [Eq. 275,276 SiX3 cat. H13C6 + HSiX3 H13C6 R cat. = N (50) Rh N Cl R Wilkinson’s catalyst [RhCl(PPh3)3], a standard catalyst for this reaction, is reported to give lower yields with less regioselectivity in these reactions.
ROMP of 1,5-cyclooctadiene (y = yield of polyoctadienamer). 55 ml of CD2Cl2; [1,5cyclooctadiene]/[catalyst] = 250:1). 39 Metal Complexes of Stable Carbenes L Ru L R Cl Cl CHPh Cl Ru L L R -L (b) (d) L L Cl Cl CHPh (a) Cl Ru (c) Cl CHPh Cl Ru CHPh R R SCHEME 11. Dominant dissociative reaction pathway that is decisive for the high catalytic performance of 52. 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.
173 After activation with MAO the catalysts produces highly branched PE which contains low- and high-molecularweight fractions. 97 Because of the high molecular weight the amount of precatalyst actually participating in the polymerization reaction is considered to be very low. 358 Generally, similar results as for the analogous phosphine complexes are obtained. 156 Polymerizations based on oleﬁn metathesis that are catalyzed by ruthenium–NHC complexes are discussed separately (vide supra). 5. Cyclopropanation of Olefins Rhodium(I) and ruthenium(II) complexes containing NHCs with hemilabile ether moieties were successfully applied as catalysts for the cyclopropanation of oleﬁns with diazoalkanes [Eq.
Advances in Organometallic Chemistry, Vol. 48 by Robert West, Anthony F. Hill