Advances in Organometallic Chemistry by Pedro J. Pérez

By Pedro J. Pérez

This e-book comprises authoritative experiences concerning the box of Organometallic Chemistry, written by way of hugely certified specialists in the zone, and reviewed through different specialists earlier than ebook. due to this excessive common, AOC is among the so much stated journals in either natural and Inorganic Chemistry fields.

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Have performed a DFT study of a series of trifluoromethyl complexes, including [Pd(CF3)Cl(dppe)],162,163 and also complexes of other metals, such as platinum(II), rhodium(I), nickel(II), copper(I), gold(I), and manganese(I), and compare the calculated structural features of these complexes with the analogous methyl derivatives. 1 gathers the experimental and calculated data for the palladium complexes. It is shown in this study that the PddC bond distances to CF3 and to CH3 are almost the same, and the distances PddP corresponding to the phosphorus atom trans to CX3 are almost equal for both groups.

11 Concentration/time data for the reaction [PdRFCl(PPh3)2] + ZnMe2 (left) and [PdRFCl(PPh3)2] + ZnMeCl (right) obtained by 19F NMR, in THF at 298 K. Note the formation of the transarylation products ZnRFMe and ZnRFCl, and the different rates or formation of transand cis-[PdRFMe(PPh3)2] in both systems. Reprinted with permission from Ref. 184. Copyright 2007 American Chemical Society. Palladium-Mediated Organofluorine Chemistry 49 observed isomerization of the isolated complexes in solution, so it must be catalyzed by ZnMeCl.

The very slow isomerization of the trans-[Pd(C6Cl2F3) (CCPh)L2] and its inability to give the cross-coupling product by reductive elimination results in its accumulation in solution. Hence, in this system, the 44 Ana C. Albéniz and Juan A. 55 Non regioselective transmetalation of the phenylethynyl group from tin to cis- or trans- [Pd(C6Cl2F3)IL2] (L ¼ PPh3). 56 Mechanism of the transmetalation step of a vinyl group from tin to [Pd (C6Cl2F3)OTfL2] (L ¼ PPh3) in polar solvents through an open transition state.

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