RT info:eu-repo/semantics/article
T1 Olefin Insertion Versus Cross-Coupling in trans-[Pd(Ar)X(AsPh3)2] Complexes (X = I, F, CF3) Treated with a Phosphine-EWOlefin Ligand to Induce Ar–X Coupling
A1 Pozo, Juan del
A1 Gioria, Estefanía
A1 Espinet Rubio, Pablo
K1 Phosphine
K1 inserción de olefina
AB Addition of the coupling promoter PEWO ligand 1-(Ph2P),2-(CH═CH–C(O)Ph)C6F4 (PhPEWO-F) to precursors with the displaceable AsPh3 ligand trans-[PdXAr(AsPh3)2] (X = I, F, CF3) fails to induce the pursued Ar–F or Ar–CF3 coupling and results in formation of products of olefin insertion into the Pd–Ar bond for X = I, CF3, and in Ar–Ar coupling for X = F. In the course of the processes, trans-[PdXAr(PhPEWO-F)(AsPh3)] intermediates are observed for X = I, F, CF3, with P-coordinated PhPEWO-F monodentate ligands and a dangling olefin group. For X = I, CF3, subsequent insertion of the double bond into the Pd–Ar bond and O-coordination gives rise to complexes with a P,C,O-pincer system. The observed insertion rates suggest that the limiting step toward insertion is the trans to cis isomerization, while insertion itself is very fast. This is supported by the fast insertion observed when PhPEWO-F is added to cis-[Pd(CF3)Ar(3-F-py)2]. The insertion mechanism in PhPEWO-F resembles the initial phase of the dearomative rearrangement mechanism reported for PdArBrL (L = dialkyl biaryl phosphine).
PB American Chemical Society
SN 0276-7333
YR 2017
FD 2017
LK http://uvadoc.uva.es/handle/10324/28847
UL http://uvadoc.uva.es/handle/10324/28847
LA eng
NO Organometallics, 2017, 36 (15), p. 2884–2890
NO Producción Científica
DS UVaDOC
RD 23-nov-2024