We have studied the oxidative addition of halogens (I2 and Br2) and interhalogens (ICl and IBr) on complexes of the type [Pd(thioquinoline)C4(COOMe)4], (thioquinoline = 8-(methylthio)quinoline, 8-(t-butylthioquinoline, 2-methyl-8-(methylthio)quinoline, 2-methyl-8-(t-butylthio)quinoline). The expected palladium(thioquinoline)-r-butadienyl derivatives have been obtained by the stoichiometric addition of I2 and Br2 to a solution of the starting palladacyclopentadienyl complexes. The bromine in excess induces the extrusion of the di-bromo-(E, E)-r-butadiene and the formation of the thioquinoline palladium(II) di-bromide species. The kinetics and mechanism of these reactions have been determined. Except for one case which was analyzed in detail by a computational study, the oxidative addition of the interhalogens ICl and IBr yields the species that is less predictable from the thermodynamic point of view. In general the computational approach justifies the reaction progress and allows an interpretative clue suggesting a kinetically governed path to the reaction products. Finally, the solid state structures of two reaction products were resolved and reported.
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|Titolo:||Addition of halogens and interhalogens on palladacyclopentadienyl complexes stabilized by pyridyl−thioether N−S spectator ligands|
|Data di pubblicazione:||2016|
|Appare nelle tipologie:||03.1 Articolo su rivista|