By Pedro J. Pérez
This booklet includes authoritative experiences in regards to the box of Organometallic Chemistry, written by way of hugely certified specialists in the region, and reviewed via different specialists sooner than ebook. due to this excessive normal, AOC is among the such a lot mentioned journals in either natural and Inorganic Chemistry fields.
- high caliber of the articles
- expertise of authors
- careful modifying that offers an easy-to-read material
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This reaction is the substitution of a halide or pseudohalide coordinated to the palladium atom by one aryl or vinyl group from an organotin derivative, but very often, it is not a single-step reaction, but a complex sequence of reactions. Because of this complexity, the stereochemistry of the substitution at the carbon and at the palladium centers and the kinetic effects of the ligands or other additives not always have a straightforward explanation. 103 In this reaction, the catalyst is the complex [Pd(C6Cl2F3)I(AsPh3)2], which in turn can be obtained by oxidative addition of C6Cl2F3I to Pd2(dba)3ÁCHCl3 in the presence of triphenylarsine.
175 Although the cross-coupling of C6F5I or C6Cl2F3I with aryl or vinyl tributyltin takes place effectively under the conditions described in Ref. 103 that is AsPh3 as ligand, the reaction performed with PPh3 is very slow, but is much more efficient with the aid of copper iodide as cocatalyst. 8 DFT calculated structures for the intermediate on the retrotransmetalation reaction [Pd(C6Cl2F3)2(ISnMe3)(AsH3)] (left) and the transition state of the transmetalation (right). Reproduced with permission from Ref.
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. 57 has been studied. 57). 183 However, DFT calculations shown that similarities are more formal than real, and that the interaction of palladium(II) with gold and tin has very few common features.
Advances in Organometallic Chemistry by Pedro J. Pérez