RT info:eu-repo/semantics/article
T1 Experimental study of the [ZnCl2(THF)2] catalyzed cis/trans-isomerization of [Pd(C6Cl2F3)Me(PPh3)2] and of the transmetalation of trans-[PdCl(C6Cl2F3)(PPh3)2] with [ZnMeCl(THF)2]
A1 Carrasco Fernández, Desiré
A1 Casares González, Juan Ángel
K1 Palladium
K1 Paladio
K1 Transmetalation
K1 Transmetalación
K1 Negishi reaction
K1 Reacción de Negishi
AB The kinetics of the transmetalation reaction between trans-[PdCl(C6Cl2F3)(PPh3)2] and [ZnMeCl(THF)2] shows a complex dependence on [PPh3] for the rate of formation of different reaction products: cis and trans-[Pd(C6Cl2F3)Me(PPh3)2], trans-[PdClMe(PPh3)] (which further reacts with [ZnClMe(THF)2]), and [Zn(C6Cl2F3)Cl(THF)2]. To better understand the system the reactions between cis and trans-[Pd(C6Cl2F3)Me(PPh3)2] and [ZnCl2(THF)2] (the retro-transmetalation reactions) and their kinetic dependence on [PPh3] were studied. These reactions lead to the formation of trans-[PdClMe(PPh3)] and [Zn(C6Cl2F3)Cl(THF)2] as main products. Additionally, the experiments show that the isomerization of cis to trans-[Pd(C6Cl2F3)Me(PPh3)2] is catalyzed by [ZnCl2(THF)2]. In this catalyzed isomerization the concentration of PPh3 is involved in two ways: It modulates the concentration of the organozinc [Zn(C6Cl2F3)Cl(THF)2], and also it shifts a ligand substitution equilibrium in the palladium complex, producing an anomalous dependence of the reaction rate on the concentration of triphenylphosphine.
PB Elsevier
SN 0020-1693
YR 2021
FD 2021
LK https://uvadoc.uva.es/handle/10324/51949
UL https://uvadoc.uva.es/handle/10324/51949
LA eng
NO Inorganica Chimica Acta, 2021, vol. 517, 120206
NO Producción Científica
DS UVaDOC
RD 23-nov-2024