A novel mixed-valence trinickel complex containing nickel(I), nickel(II) and iodonium moieties

摘要

The title complex, [{Ni(C14H28N2S2)(2)}NiI2]I-+(-). CH3CN forms as a crystalline minor product in the oxidation of Ni(C14H28N2S2) with iodine. X-ray analysis reveals that the trinuclear monocations are racemic and consist of two neutral, square-planar Ni(II)N(amine)(2)S(thiolate), units bridged via the thiolate ligands by an unusual NiI2+ group that call be described as Containing P ii(I) and I(I) species. The Ni(I) atom is coordinated to two S(thiolate) ligands, an iodide ligand and an iodonium atom in an unusual distorted trigonal-pyramidal arrangement. The I(I) ion is coordinated to the remaining two S(thiolate) ligands [S-I-S = 171.91(7)degrees] and to the Ni(I) ion [Ni(I)-I(I)= 3.0298(14) Angstrom] to yield a T-shaped geometry. Pyramidal coordination at the four sulfur atoms gives each cation a U-shaped conformation in profile. (C) 2001 Elsevier Science B.V. All rights reserved. [References: 34]