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Digold(I) Thianthrenyl Complexes. Effect of Diphosphine Ligands on Molecular Structures in the Solid State and in
Ryota Abe1, Yoshitaka Tsuchido1, Tomohito Ide2
1Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
Abstract:
A series of digold complexes possessing two thianthrenyl ligands, Au2(Thi)2(Ph2P(CH2) PPh2) (Thi: 1-thianthrenyl; 1: n = 1, 2: n = 2, 3: n = 3, 4: n = 4), were prepared and characterized by crystallographic and spectroscopic measurements. X-ray crystallography of complexes 1 and 3 revealed U-shaped structures with short Au-Au distances [3.2171(3) Å and 3.0735(2) Å]. Complex 2 and three of the four structure-determined molecules of complex 4 showed structures without Au-Au contacts. UV-vis spectroscopic measurements of 1-4 and TD-DFT calculations of the two conformers of 1 revealed that complexes 1 and 3 in the solution phase contained conformers with Au(I)-Au(I) interactions in a much higher proportion than complexes 2 and 4. As a result, complexes with diphosphine ligands containing an odd number of methylene groups preferred structures with Au-Au interactions in the solid state and in solution. Oxidation of 1 with 2 equiv of PhICl2 yielded a mixture of monomeric and dimeric thianthrenes and its dimer via ligand elimination and C-C coupling, respectively.
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