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Título
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]
Año del Documento
2021
Editorial
Elsevier
Descripción
Producción Científica
Documento Fuente
Inorganica Chimica Acta, 2021, vol. 517, 120206
Abstract
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.
Palabras Clave
Palladium
Paladio
Transmetalation
Transmetalación
Negishi reaction
Reacción de Negishi
ISSN
0020-1693
Revisión por pares
SI
Patrocinador
Ministerio de Economía, Industria y Competitividad (project CTQ2016-80913-P)
Ministerio de Ciencia e Innovación (project PID2019-111406GB-100)
Junta de Castilla y León (projects VA051P17 and VA062G18)
Ministerio de Ciencia e Innovación (project PID2019-111406GB-100)
Junta de Castilla y León (projects VA051P17 and VA062G18)
Propietario de los Derechos
© 2021 Elsevier
Idioma
eng
Tipo de versión
info:eu-repo/semantics/acceptedVersion
Derechos
openAccess
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