Issue 5, 2012
From the journal:

RSC Advances

Platinum(ii) and palladium(ii) complexes derived from 1-ferrocenylmethyl-3,5-diphenylpyrazole. Coordination, cyclometallation or transannulation?†

Concepción López,*a   Asensio González,b   Ramon Bosque,a   Pradipta K. Basu,ab   Mercè Font-Bardíac  and  Teresa Calvetd  

* Corresponding authors

a Departament de Química Inorgànica, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11. E-08028-Barcelona, SPAIN

b Laboratori de Química Orgánica, Facultat de Farmacia, Universitat de Barcelona, Pl. Pius XII s/n. E-08028-Barcelona, SPAIN

c Unitat de Difracció de Raigs-X. Centre Científic i Tecnològic de la Universitat de Barcelona. Universitat de Barcelona, Solé i Sabaris 1-3, 08028-Barcelona, SPAIN

d Departament de Cristal·lografia Mineralogía i Dipòsits Minerals. Facultat de Geologia. Universitat de Barcelona, Martí i Franquès s/n. E-08028-Barcelona, SPAIN

Abstract

The synthesis and characterization of the novel pyrazole derivative [1-(Fc–CH2)-3,5-Ph2–(C3HN2)] (2) {Fc = (η5–C5H5)Fe(η5–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 Na2[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)}Cl2(dmso)] (3), the cis- isomers of [M{1-(Fc–CH2)-3,5-Ph2–(C3HN2)}Cl2(dmso)] {M = Pt (4) or Pd (7)}, trans-[Pd{1-(Fc–CH2)-3,5-Ph2–(C3HN2)}2Cl2] (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-[(η5–C5H4)Fe{(η5–C5H4)–CH2]-3,5-Ph2–(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(sp2, phenyl) in 9 or the C(sp2, 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 Na2[PdCl4] and NaAcO density functional theory (DFT) calculations of the complexes have also been carried out.

Graphical abstract: Platinum(ii) and palladium(ii) complexes derived from 1-ferrocenylmethyl-3,5-diphenylpyrazole. Coordination, cyclometallation or transannulation?

About
Cited by
Related
Download options Please wait...

Supplementary files

Article information

DOI
https://doi.org/10.1039/C1RA01080H
Article type
Paper
Submitted
14 Nov 2011
Accepted
16 Nov 2011
First published
10 Jan 2012

RSC Adv., 2012,2, 1986-2002

Permissions

Request permissions

Platinum(II) and palladium(II) complexes derived from 1-ferrocenylmethyl-3,5-diphenylpyrazole. Coordination, cyclometallation or transannulation?

C. López, A. González, R. Bosque, P. K. Basu, M. Font-Bardía and T. Calvet, RSC Adv., 2012, 2, 1986 DOI: 10.1039/C1RA01080H

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements