TRIORGANOPHOSPHINEGOLD(I) COMPLEXES OF PYRIDINE-2-THIONATE AND PYRIMIDINE-2-THIONATE

Triorganophosphinegold(I) complexes of the anions derived from pyridine-2-thione (2-pySH) and 1H-pyrimidine-2-thione (2-pymSH), [Au(PR3)(SR')] (R = Et, Ph or C6H11), have been prepared and characterized by spectroscopic (IR, H-1 and C-13 NMR and fast atom bombardment MS) methods and for the PPh3 compounds by X-ray crystallographic techniques. The mononuclear compounds feature linear gold atom geometries defined by P and S atoms with important parameters for [Au(PPh3)(2-pyS)]: Au-P 2.258(1), Au-S 2.297(2) angstrom and P-Au-S 177.9(1)degrees and for [Au(PPh3)(2-pymS)]: Au-P 2.253(2), Au-S 2.310(3) angstrom and P-Au-S 174.7(1)degrees. The [Au(PPh3)(2-pyS)] complex 2 crystallizes in the monoclinic space group P2(1)/c with unit-cell dimensions a = 12.235(1), b = 10.009(2), c = 1 7.292(2) angstrom, beta = 104.08(1)degrees and Z = 4; [Au(PPh3)(2-pymS)] 5 crystallizes in the triclinic space group P1BAR with a = 11.006(2), b = 11.356(4), c = 8.873(1) angstrom, alpha = 109.85(2), beta = 95.72(1), gamma = 93.55(2)degrees and Z = 2. The structures were refined to final R = 0.025 for 2527 reflections with I greater-than-or-equal-to 2.5sigma(I) and R = 0.057 for 3416 reflections with I greater-than-or-equal-to 2.5sigma(I) for 2 and 5, respectively.