By Robert West, Anthony F. Hill
Just about all branches of chemistry and fabric technological know-how now interface with organometallic chemistry-the learn 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 largely acclaimed serial includes authoritative stories that tackle all features of organometallic chemistry, a box which has multiplied drastically because the ebook of quantity 1 in 1964.
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Extra resources for Advances in Organometallic Chemistry, Vol. 48
232 Due to its convenience and the broad range of complexes accessible, this method is very likely to gain an important role as a synthetic route to NHC complexes. t. t. - 2 AgBr - 2 CH3CN R N PdCl2 N R 2 (33) 28 HERRMANN et al. 64 d. Rare examples. 233,234 The electrochemical oxidation of chromium(0), molybdenum(0), and tungsten(0) NHC complexes is possible. 235,236 The oxidative addition of a suitable substrate equals a two-electron oxidation. , [(L)AuCl] (L = Me2 S, PPh3 tetrahydrothiophene) and subsequently be quenched by HCl to give a 3-hydroimidazolin-2-ylidene complex [Eq.
102 In general, ionic liquids are novel reaction media for homogeneous catalysis. 347,348 Metal Complexes of Stable Carbenes 47 4. Mechanism Studies regarding the nature of the catalytically active species for NHC complexes in Heck-type reactions have focused on the Mizoroki–Heck reaction and have consistently revealed a palladium(0) species as the active catalyst. 350 C. Other Reactions NHCs have as well been tested in a variety of other reactions. In most of these transformations, they were not found to be real alternatives to other ligand classes, but it has to be taken into account that only a small number of structurally different stable carbenes have been investigated so far.
The catalyst development with these metals has focused in particular on Heck-type reactions, especially the Mizoroki–Heck reaction itself [Eq. (42)]315–318 and various cross coupling reactions [Eq. 323–325 Related reactions like the Sonogashira coupling [Eq. (44)]326–329 and the Buchwald– Hartwig amination [Eq. (45)]330–333 were also successfully performed with these types of catalysts. [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.
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