RT info:eu-repo/semantics/article
T1 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
A1 Villar, Pedro
A1 Pérez Temprano, Mónica H.
A1 Casares González, Juan Ángel
A1 Álvarez, Rosana
A1 Espinet Rubio, Pablo
A1 Villar, Pedro
AB 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.
PB American Chemical Society
SN 0276-7333
YR 2020
FD 2020
LK http://uvadoc.uva.es/handle/10324/42910
UL http://uvadoc.uva.es/handle/10324/42910
LA spa
NO Organometallics 2020, 39, 12, 2295–2303
NO Producción Científica
DS UVaDOC
RD 08-nov-2024