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Título
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
Año del Documento
2017
Editorial
American Chemical Society
Descripción
Producción Científica
Documento Fuente
Organometallics, 2017, 36 (15), p. 2884–2890
Résumé
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).
Palabras Clave
Phosphine
inserción de olefina
ISSN
0276-7333
Revisión por pares
SI
Patrocinador
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)
Junta de Castilla y León (programa de apoyo a proyectos de investigación – Ref. VA256U13)
Version del Editor
Propietario de los Derechos
© 2017 American Chemical Society
Idioma
eng
Derechos
openAccess
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