Palladium arenethiolates with intramolecularly coordinating nitrogen lewis bases
- 1 January 1996
- journal article
- research article
- Published by Wiley in Recueil des Travaux Chimiques des Pays-Bas
- Vol. 115 (5) , 286-292
- https://doi.org/10.1002/recl.19961150505
Abstract
The reaction of [PdCl2(MeCN)2] with one or two equivalents of Me3SiSC6H4NMe2‐2 in toluene affords the mono(arenethiolate) complex [PdCl(SC6H4NMe2‐2)] (1) or the bis(arenethiolate) complex [Pd(SC6H4NMe2‐2)2] (2), respectively, in high yields. [PdCl(SC6H4NMe2‐2)] (1) exists as a tetramer in the solid state (X‐ray) while [Pd(SC6H4NMe2‐2)2] (2) is a monomer both in the solid state and in solution (cryoscopy, NMR). The X‐ray structure determination of tetrameric 1 shows arenethiolate ligands bridging between PdCl units to form a unique eight‐membered U‐shaped Pd4S4 ring. Crystals of 1 are tetragonal, space group magnified image , with a = b = 12.0495(10) Å, c = 16.672(1) Å, V= 2420.6(3) Å3, Z = 2, and final R = 0.029, wR = 0.034 and S = 1.42 for 1174 reflections with I > 2.5 σ(I) and 111 variables. The X‐ray structure determination of 2 shows it to be monomeric in the solid state. The palladium has a square‐planar geometry that results from coordination by two S,N‐chelating arenethiolate ligands with a trans S and trans N arrangement of the donor atoms. Crystals of 2 are triclinic, space group magnified image , with a = 8.9923(5) Å, b = 9.2472(5) Å, c = 11.5933(6) Å, V = 825.93(9) Å3, Z = 2, and final R = 0.025, wR = 0.047 and S = 0.53 for 3603 reflections with I > 2.5 σ(I) and 226 variables.Funding Information
- Netherlands Foundation for Chemical Research
- Netherlands Organization for Scientific Research
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