2026-05-05T11:17:40Zhttps://uvadoc.uva.es/oai/request

oai:uvadoc.uva.es:10324/288472025-03-26T16:41:31Zcom_10324_1186com_10324_931com_10324_894com_10324_28542com_10324_952col_10324_1404col_10324_28543

Pozo, Juan del Gioria, Estefania Espinet Rubio, Pablo 2018-03-01T08:28:19Z 2018-03-01T08:28:19Z 2017 Organometallics, 2017, 36 (15), p. 2884–2890 0276-7333 http://uvadoc.uva.es/handle/10324/28847 10.1021/acs.organomet.7b00353 Producción Científica 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). Ministerio de Economía, Industria y Competitividad (Projects CTQ2014-52796-P, CTQ2016-80913-P, and CTQ2014-52974-REDC) Junta de Castilla y León (programa de apoyo a proyectos de investigación – Ref. VA256U13) application/pdf eng American Chemical Society info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ © 2017 American Chemical Society Attribution-NonCommercial-NoDerivatives 4.0 International Phosphine inserción de olefina 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 info:eu-repo/semantics/article https://pubs.acs.org/doi/ipdf/10.1021/acs.organomet.7b00353 SI