Synthesis of the first monodentate S- and O-coordinating 1,3,5-triaza-7-phosphaadamantane-7-chalcogenides [CoCl(bpy)2 (Z-PTA=Z)]X (Z=S, O; bpy=2,2′-bipyridine; X = BF4, PF6) and [COCl(bpy)2(N-PTA)]BF4 (PTA=1,3,5-triaza-7-phosphaadamantane)

The Coll compounds [CoCl(bpy)(2)(S-PTA=S)]X, [CoCl(bpy)(2)(O-PTA=O)]X [PTA=S = 1,3,5-triaza-7-phosphaadamantane-7-sulfide (1); PTA=O = 1,3,5-triaza-7-phosphaadamantane-7-oxide (2); bpy = 2,2'-bipyridine; X = BF4 (1a, 2a), X = PF6 (1b, 2b)] and (CoCl(bpY)(2)(N-PTA)BF4 have been prepared by reacting anhydrous CoCl2 with PTA=S, PTA=O and PTA, respectively, in ethanol at room temperature in presence of bpy and NaBF4 or NaPF6. They are soluble in polar solvents such as water and Me2SO, and have been characterized by IR, H-1, P-31{H-1) NMR, ESI-MS, elemental analyses and (for 2a) single crystal X-ray diffraction structural analysis. The molecular structures bear two molecules of bpy and one PTA=Z. Compounds 1a and 1b represent the first reported transition metal complexes of PTA=S and additionally 1 and 2, are the first examples of transition metal complexes bearing both bpy (or any polypyridyl) and PTA-cage ligands. (C) 2010 Elsevier Ltd. All rights reserved.