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oai:uvadoc.uva.es:10324/429542025-02-17T13:52:22Zcom_10324_1186com_10324_931com_10324_894col_10324_1404
UVaDOC author Casares González, Juan Ángel author Pérez Iglesias, María author Infante Blanco, Rebeca author Espinet Rubio, Pablo 2020-10-14T11:35:47Z 2020-10-14T11:35:47Z 2019 Organometallics 2019, 38, 19, 3688–3695 http://uvadoc.uva.es/handle/10324/42954 10.35376/10324/42954 ABSTRACT: Ligand PPh2(p-C6H4-C6F5), LHF, is an example of monodentate biphenyl phosphine that allows for cis coor-dination of two phosphines to Pd, as in complex cis-[Pd(C6F5)2Pd(LHF)2] (A). At 25 °C complex A undergoes easy reductive elimination to decafluorobiphenyl and, competitively, isomerizes to trans-[Pd(C6F5)2Pd(LHF)2] via a 3-coordinated interme-diate [Pd(C6F5)2Pd(LHF)]. Unexpectedly the direct reductive C6F5–C6F5 elimination is faster from the 4-coordinated complex A than from the 3-coordinated intermediate. The reason of this is that two cis LHF ligands play the role of a chelate with a large bite angle with tetrahedral distortion. As a matter of fact, using LHF in excess gives ΔG‡Pf-Pf = 23.1 kcal.mol-1, which ranks its efficiency for coupling and formation of the corresponding Pd0 catalyst as better than XantPhos or PhPEWO-F, and about the same as tBuBrettPhos. On the other hand, complex (µ-Cl)2[Pd2(C6F5)2(LHF)2] (B), obtained by reaction of (µ-Cl)2[Pd2(C6F5)2(tht)2] with LHF, presents in the 19F NMR COSY spectrum a very intriguing through space coupling pattern of the Fortho atoms of the C6F5 group in LHF and the C6F3Cl2-3,5 group on Pd. The inter-mitent coupling mechanism proposed is based on the switching of π-π stacking of C6F5 with one or another Ph group of LHF, which gives rise to enantiomers at the chiral P atom. Rotation around the P–biphenyl bond under hindrance of rotation around the C–C6F5 bond produces the intriguing selective coupling observed. eng The intriguing behavior of an apparently simple coupling promoter ligand, PPh2(p-C6H4-C6F5), in their Pd complexes info:eu-repo/semantics/article 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