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

✍ Scribed by Stephen Fox; Robert T Stibrany; Joseph A Potenza; Harvey J Schugar

Book ID
104138470
Publisher
Elsevier Science
Year
2001
Tongue
English
Weight
138 KB
Volume
316
Category
Article
ISSN
0020-1693

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✦ Synopsis

The title complex, [{Ni(C 14 H 28 N 2 S 2 ) 2 }NiI 2 ] + I -•CH 3 CN forms as a crystalline minor product in the oxidation of Ni(C 14 H 28 N 2 S 2 ) 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) 2 units bridged via the thiolate ligands by an unusual NiI 2 + group that can be described as containing Ni(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)°] and to the Ni(I) ion [Ni(I) I(I)= 3.0298(14) A , ] to yield a T-shaped geometry. Pyramidal coordination at the four sulfur atoms gives each cation a U-shaped conformation in profile.

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