PALLADIUM ARENETHIOLATES WITH INTRAMOLECULARLY COORDINATING NITROGEN LEWIS-BASES

The reaction of [PdCl2(MeCN)(2)] with one or two equivalents of Me(3)S iSC(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 an d in solution (cryoscopy, NMR). The X-ray structure determination of t etrameric 1 shows arenethiolate ligands bridging between PdCl units to form a unique eight-membered U-shaped Pd4S4 ring. Crystals of 1 are t etragonal, space group P (4) over bar 2(1)c, with a = b = 12.0495(10) Angstrom, c = 16.672(1) Angstrom, V = 2420.6(3) Angstrom(3), Z = 2, an d final R = 0.029, wR = 0.034 and S = 1.42 for 1174 reflections with I > 2.5 sigma(I) and 111 variables. The X-ray structure determination o f 2 shows it to be monomeric in the solid state. The palladium has a s quare-planar geometry that results from coordination by two S,N-chelat ing arenethiolate ligands with a trans S and trans N arrangement of th e donor atoms. Crystals of 2 are triclinic, space group P (1) over bar , with a = 8.9923(5) Angstrom, b = 9.2472(5) Angstrom, c = 11.5933(6) Angstrom, V = 825.93(9) Angstrom(3), Z = 2, and final R = 0.025, wR = 0.047 and S = 0.53 for 3603 reflections with I > 2.5 sigma(I) and 226 variables.