Files
Document type
ArticleVersion
Accepted versionPublication date
All rights reserved
Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/211288
Platinum(II) and palladium(II) complexes derived from 1-ferrocenylmethyl-3,5-diphenylpyrazole. Coordination, cyclometallation or transannulation?
Journal Title
Director/Tutor
Journal ISSN
Volume Title
Related resource
Abstract
The synthesis and characterization of the novel pyrazole derivative [1-(Fc-CH2)-3,5-Ph-2-(C3HN2)] (2) {Fc = (eta(5) -C5H5)Fe(eta(5)-C5H4)-} with a ferrocenylmethyl substituent on position 1 of the heterocycle is described. The study of the reactivity of 2 with cis-[MCl2L2] (M = Pt and L = dmso or M = Pd and L = dmso or CH3CN), Pd(AcO)(2) or Na-2[PdCl4] under different experimental conditions, has allowed us to isolate and characterize a wide variety of platinum(II) or palladium(II) complexes: trans-[Pt{1-(Fc-CH2)-3,5-Ph2-(C3HN2)} Cl-2(dmso)] (3), the cis-isomers of [M{1-(Fc-CH2)-3,5-Ph-2-(C3HN2)}Cl-2(dmso)] {M = Pt (4) or Pd (7)}, trans-[Pd{1-(Fc-CH2)-3,5-Ph-2-(C3HN2)}(2)Cl-2] (8), the cyclometallated compounds [M{1-(Fc-CH2)-(3-C6H4)-5-Ph-(C3HN2)}Cl(L)] {with M = Pt and L = dmso (5) or PPh3 (6) or M = Pd and L = PPh3 (9)} and the palladium(II) complex [Pd{1-[(eta(5)-C5H4)Fe{(eta(5)-C5H4)-CH2]-3,5-Ph-2-(C3HN2)}Cl(PPh3)] (10) that arises from a transannulation process. The crystal structures of the free ligand 2 and compounds 4, 7, 9 and 10 are also reported and confirm the cis-disposition of the Cl- ligands in 4 and 7, the trans-arrangement of the phosphorous and the nitrogen atoms in 9 and 10, the mode of binding of the ligand in 4, 7, 9 and 10 and the nature of the metallated carbon atom {C(sp(2), phenyl) in 9 or the C(sp(2), ferrocenyl) of the C5H5 ring in 10}. In order to rationalize the different nature of the products isolated in the reactions of 2 with Pd(AcO)(2) or Na-2[PdCl4] and NaAcO density functional theory (DFT) calculations of the complexes have also been carried out.
Subject (English)
Citation
Citation
LÓPEZ MARTÍNEZ, Ma. Concepción, et al. Platinum(II) and palladium(II) complexes derived from 1-ferrocenylmethyl-3,5-diphenylpyrazole. Coordination, cyclometallation or transannulation?. RSC Advances. 2012. Vol. 2, num. 5, pags. 1986-2002. ISSN 2046-2069. [consulted: 17 of August of 2026]. Available at: https://hdl.handle.net/2445/211288