Issue 47, 2022

Palladium(ii) ortho-cyano-aminothiophenolate (ocap) complexes

Abstract

A series of Pd(II) complexes containing ortho-cyano-aminothiophenolate (ocap) ligands have been prepared and their molecular structures elucidated. Hg(II) ocap complexes, [Hg{SC6H3XN(C[triple bond, length as m-dash]N)}]n (X = H, Me) (1), react with Na2S to afford HgS and Na2[ocap] which reacts in situ with K2[PdCl4] to afford palladium ocap complexes [Pd{SC6H3XN(C[triple bond, length as m-dash]N)}]n (2). A second route to these coordination polymers has also been developed from reactions of 2-aminobenzothiazole (abt) complexes, trans-PdCl2(abt)2 (3), with NaOH. We have not been able to crystallographically characterise coordination polymers 2, but addition of PPh3, a range of phosphines and cyclic diamines affords mono and binuclear complexes in which the ocap ligand adopts different coordination geometries. With PPh3, binuclear [Pd(μ-κ21-ocap)(PPh3)]2 (4) results, in which the ocap bridges the Pd2 centre acting as an S,N-chelate to one metal centre and binding the second via coordination of the cyanide nitrogen. In contrast, with diphosphines, Ph2P(CH2)nPPh2 (n = 1–4), mononuclear species predominate as shown in the molecular structures of Pd(κ2-ocap){κ2-Ph2P(CH2)nPPh2} (5–7; n = 1–3). With 2,2′-bipy and 1,10-phen we propose that related monomeric chelates Pd(κ2-ocap)(κ2-bipy) (9) and Pd(κ2-ocap)(κ2-phen) (10) result but we have been unable to substantiate this crystallographically. Addition of HgCl2(phen) to 9a (generated in situ) affords heterobimetallic Pd(κ2-phen)(μ-κ21-ocap)HgCl22-phen) (11), in which Hg(II) is coordinated through the ring sulfur.

Graphical abstract: Palladium(ii) ortho-cyano-aminothiophenolate (ocap) complexes

Supplementary files

Article information

Article type
Paper
Submitted
16 Aug 2022
Accepted
10 Nov 2022
First published
11 Nov 2022
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2022,51, 18136-18142

Palladium(II) ortho-cyano-aminothiophenolate (ocap) complexes

S. A. Al-Jibori, A. S. Al-Janabi, A. A. Irzoqi, A. I. A. Abdullah, S. Basak-Modi, G. R. F. Orton, S. Ghosh, C. Wagner and G. Hogarth, Dalton Trans., 2022, 51, 18136 DOI: 10.1039/D2DT02681C

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, 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 commercial 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