By Pedro J. Pérez
This ebook comprises authoritative studies concerning the box of Organometallic Chemistry, written via hugely certified specialists in the sector, and reviewed by means of different specialists ahead of e-book. due to this excessive usual, AOC is without doubt one of the such a lot brought up journals in either natural and Inorganic Chemistry fields.
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Extra info for Advances in Organometallic Chemistry
CF3 F OSO2CF3 54 Ana C. Albéniz and Juan A. 62 Competing reductive elimination product depending on the oxidant used. 63 Reductive elimination mechanism in a triflato palladium(IV) complex. concentration of triflate, suggesting a predissociation equilibrium of this anion; in fact, the replacement of this anion by PF6 À produces a significant increase in the decomposition rate. 8) cal molÀ1 KÀ1, support a mechanism in which one ligand has left the coordination sphere during or previously to the rate-determining step.
Thus, the reductive elimination from Pd(IV) seems to be kinetically much easier than from Pd(II). Remarkably, the reaction does not produce other reductive elimination products such as ArdF. 200 First, they demonstrated that, as expected, the reductive elimination of ArdCF3 does not take place from the Pd(II) complex [PdAr(CF3)(LL)]. Heating the complex [Pd(CF3)(4-F-C6H4)(dtbpy)] at 130 C for 72 h only a 5% of the cross-coupling product CF3dC6H4F was obtained. 62). For instance, the use of N-bromo-succinimide produces the elimination of ArdBr as a major product.
177 By this route, the transmetalation to trans[PdRFXL2] gives the trans-[PdRFR0 L2] isomer. For L ¼ PPh3, RF ¼ C6Cl2F3 and R0 ¼ vinyl, this isomer has been detected in solution, reinforcing the mechanistic proposal. 54) transition states, provides a satisfactory explanation for the observed lack of selectivity during the transmetalation for the abovementioned alkynyltin derivatives, which can follow the cyclic pathway but, being good ligands and thus capable of removing iodine from the coordination sphere of the palladium, could also follow the open pathway.
Advances in Organometallic Chemistry by Pedro J. Pérez