Keily Heredia
Published: 2006
Total Pages: 136
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The tetradentate thioether Si(CH[subscript]2SBu[superscript]t)[subscript]4 was used to synthesize the complete series of copper(I) complexes Cu[subscript]2Si(CH[subscript]2SBu[superscript]t)[subscript]4X[subscript]2 (X = C1, Br, I). Interestingly, a single X-ray diffraction study of the chloro derivative revealed the presence of both four-coordinate tetrahedral and three-coordinate trigonal planar copper centers. The adamantyl-substituted dithioether Me[subscript]2Si(CH[subscript]2SAd)[subscript]2 has been readily synthesized and it is the first member of the Me[subscript]2Si(CH[subscript]2SR)[subscript]2 (R = alkyl, aryl) family of ligands to be structurally characterized. Reactivity studies towards monovalent coinage metal ions have produced simple 1:1 and 1:2 complexes {Me[subscript]2Si(CH[subscript]2SAd)[subscript]2}CuX (X = C1, Br, I), and [Cu{Me[subscript]2Si(CH[subscript]2SAd)[subscript]2}[subscript]2]PF[subscript]6. Significantly, the bulky substituents on the thioether preclude the generation of polymeric species such as those isolated for R = Me and result instead in the formation of rare examples of three-coordinate trigonal planar Cu(I) thioether complexes. Furthermore, these are the first such complexes exhibiting [CuS[subscript]2X] coordination spheres. In a similar vein, the dinuclear gold complexes Au[subscript]2{Me[subscript]2Si(CH[subscript]2SAd)[subscript]2}X[subscript]2 (X = C1, Br), each of which displays a fairly strong intramolecular Au...Au aurophilic interaction, are obtained instead of the polymeric species isolated for closely related but less sterically demanding thioether ligands [e.g., Me[subscript]2Si(CH[subscript]2SMe)[subscript]2]. The new complexes have been characterized by a variety of analytical and spectroscopic techniques, including electrospray ionization mass spectroscopy (ESIMS). An overview of the coordination chemistry of Me[subscript]2Si(CH[subscript]2SAd)[subscript]2 towards other transition metal ions such as Ag(I), Cd(II) and Hg(II) will be also discussed.