Palladium arenethiolates with intramolecularly coordinating nitrogen lewis bases

✍ Scribed by Maurits D. Janssen; David M. Grove; Gerard van Koten; Anthony L. Spek

• Book ID: 104589861
• Publisher: Elsevier Science
• Year: 2010
• Tongue: English
• Weight: 689 KB
• Volume: 115
• Category: Article
• ISSN: 0165-0513
• DOI: 10.1002/recl.19961150505

✦ Synopsis

Abstract

The reaction of [PdCl~2~(MeCN)~2~] with one or two equivalents of Me~3~SiSC~6~H~4~NMe~2~‐2 in toluene affords the mono(arenethiolate) complex [PdCl(SC~6~H~4~NMe~2~‐2)] (1) or the bis(arenethiolate) complex [Pd(SC~6~H~4~NMe~2~‐2)~2~] (2), respectively, in high yields. [PdCl(SC~6~H~4~NMe~2~‐2)] (1) exists as a tetramer in the solid state (X‐ray) while [Pd(SC~6~H~4~NMe~2~‐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 Pd~4~S~4~ 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) Å^3^, 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) Å^3^, 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.