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Título
Experimental and DFT Study of the [AuAr(AsPh3)]-Catalyzed cis/trans Isomerization of [PdAr2(AsPh3)2] (Ar = C6F5 or C6Cl2F3): Alternative Mechanisms and Its Switch upon Pt for Pd Substitution
Autor
Año del Documento
2020
Editorial
American Chemical Society
Documento Fuente
Organometallics 2020, 39, 12, 2295-2303
Abstract
The aryl transmetalation processes between cis-[PdRf2(AsPh3)2] (Rf = C6Cl2F3) and [AuPf(AsPh3)] (Pf = C6F5) has been studied experimentally and by DFT calculations. Aryl exchange with or without isomerization of the Pd geometry occurs by ligand displacement of one AsPh3 ligand by an [AuAr(AsPh3)] molecule, which coordinates using the Au–Ar bond electron density, followed or not by a second switch to the next aryl (Ar) group. The transition states are bridged Ar–Au(AsPh3)–Ar′ structures with fairly planar geometries. Alternatively, a direct switch of the Au(AsPh3) fragment to either cis or trans Ar groups on Pd can be achieved from a square-pyramidal [(AsPh3)Au-PdAr3(AsPh3)] intermediate or transition state. The later pathway is less favorable for the case studied (M = Pd), but it is preferred for the same chemical system with M = Pt. The study provides some clues on exchanges that can be relevant in organic syntheses catalyzed by bimetallic systems.
Materias (normalizadas)
ISSN
0276-7333
Revisión por pares
SI
Patrocinador
MINECO (CTQ2016-80913-P y CTQ2017-89217-P), Junta de Castilla y León (VA051P17 y VA062G18), Xunta de Galicia (Consolidación GRC ED431C2017/61)
Idioma
eng
Tipo de versión
info:eu-repo/semantics/submittedVersion
Derechos
embargoedAccess
Collections
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