Heterotopic assemblage of two different disk-shaped ligands through trinuclear silver(I) complexation: ligand exchange-driven molecular motion.

نویسندگان

  • Shuichi Hiraoka
  • Motoo Shiro
  • Mitsuhiko Shionoya
چکیده

The sandwich-shaped heterotopic trinuclear Ag+ complex Ag(3)1.2 was exclusively formed from two different tris(thiazolyl) and hexa(thiazolyl) disk-shaped ligands, 1 and 2, with the aid of three Ag+ ions. The variable-temperature 1H NMR study on its complexation behavior revealed that metal-ligand exchanges between the two neighboring thiazolyl nitrogen donors of 2 take place at the three Ag+ centers in concert. DeltaH++ and DeltaS++ for the exchange process were calculated to be 50.5 kJ mol(-1) and -26.7 J mol(-1) K(-1), respectively, and its energy barrier at 298 K was estimated to be 58.5 kJ mol(-1). Each concerted metal-ligand exchange leads to an intramolecular 60 degrees-rotational motion ((P) <==>(M) conversion) between the two disk-shaped ligands.

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عنوان ژورنال:
  • Journal of the American Chemical Society

دوره 126 4  شماره 

صفحات  -

تاریخ انتشار 2004