Advances in Organometallic Chemistry, Vol. 48 - download pdf or read online

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 examine of compounds containing carbon-metal bonds. Organometallic compounds diversity from species that are so reactive that they just have a temporary lifestyles at ambient temperatures to species that are thermally very reliable. This commonly acclaimed serial includes authoritative experiences that deal with all elements of organometallic chemistry, a box which has accelerated vastly because the e-book of quantity 1 in 1964.

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Additional resources for Advances in Organometallic Chemistry, Vol. 48

Sample text

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.

Pd] + X R base X [M] + HX (42) + [M]X (43) R + HX (44) R [Pd] or [Ni] R + R X H [Pd] + R base [Pd] or [Ni] NH + X R N R + HX base [M] = B(OH)2, SnR3, MgX, ZnX, Si(OR)3 (45) X = I, Br, Cl, OSO2CF3, N2+, C(O)Cl 43 Metal Complexes of Stable Carbenes The mechanistic similarity of these reactions is based on the identity of the first step of the catalytic cycle: the oxidative addition of the aryl halide to a palladium(0) species [Eq. (46)]. Electron-donating ligands like trialkyl phosphines as well as NHCs facilitate the oxidative addition of aryl halides; making the ligands sterically demanding has shown in many cases an additional accelerating effect on catalysis, which is mostly accounted to influences on subsequent reaction steps.

L1 L1 Cl Cl Ru Cl CH2 Cl CH2 + L2 Ru (41) L2 As a consequence of the higher coordination energy, the dicarbene complexes 53 disfavor a dissociative pathway similar to that of 52. A mixed NHC/phosphine complex of type 54, however, reveals a phosphine dissociation energy in the same order of magnitude as 52. Therefore, 54 is able to populate the dissociative pathway just as readily as 52. In contrast to 52, however, a phosphine-free species 58 is to be considered as the key intermediate in the catalytic cycle.

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


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