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Issue 17, 2012
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Reaction of a heterotopic P,SAs ligand with group 10 metal(ii) complexes: As–S bond cleavage and the formation of two unusual trinuclear structural isomers for Pd and Pt

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Abstract

The synthesis of the heterotopic P,SAs ligand, 1-Ph2AsSC6H4-2-PPh2 (1) and its reaction with [PdCl2(cod)], [PtI2(cod)] (cod = 1,5-cyclooctadiene) and NiCl2·6H2O is reported. Cleavage of the As–S bond of 1 and coordination of the resulting phosphanylthiolato ligand (SC6H4-2-PPh2) (SC6H4-2-PPh2 = P,S) was observed with formation of [M(P,S)2] (M = Ni, Pd, Pt). In the case of Pd and Pt, not only the mononuclear complexes [M(P,S)2] formed, but also the trimers of [MX(P,S)] ([MX{(μ-S-SC6H4-2-PPh2)-κ2S,P}]3 [M = Pd, X = Cl (2) and M = Pt, X = I (4)]). Formation of 2 and 4 was preceded by the trinuclear isomeric intermediates [(cis-M{(μ-S-SC6H4-2-PPh2)-κ2S,P}2)-MX2-MX{(μ-S-SC6H4-2-PPh2)-κ2S,P}] [M = Pd, X = Cl (3) and M = Pt, X = I (5)]. The crystal structures of 1–5 and a possible reaction mechanism that leads to 2 and 4 are presented.

Graphical abstract: Reaction of a heterotopic P,SAs ligand with group 10 metal(ii) complexes: As–S bond cleavage and the formation of two unusual trinuclear structural isomers for Pd and Pt

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Supplementary files

Article information


Submitted
29 Dec 2011
Accepted
01 Feb 2012
First published
01 Feb 2012

Dalton Trans., 2012,41, 5326-5333
Article type
Paper

Reaction of a heterotopic P,SAs ligand with group 10 metal(II) complexes: As–S bond cleavage and the formation of two unusual trinuclear structural isomers for Pd and Pt

I. Sárosi, A. Hildebrand, P. Lönnecke, L. Silaghi-Dumitrescu and E. Hey-Hawkins, Dalton Trans., 2012, 41, 5326
DOI: 10.1039/C2DT12506D

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