Tin-Capped Trinuclear Nickel Clusters: Redox Isomerism between μ3-Stannyl and μ3-Stannylene Clusters of the Class [Ni3(dppm)3(μ3-I)(μ3-SnClx)]n+ (x = 2, n = 1; x = 3, n = 0)
- 30 July 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 41 (17) , 4306-4308
Abstract
The reaction of Ni3(dppm)3(μ3-I)2 with sodium trichlorostannate affords the first tin-capped nickel cluster Ni3(dppm)3(μ3-I)(μ3-SnCl3) (1). A site of coordinative unsaturation at tin can be introduced by the reaction of 1 with Tl[PF6] yielding the stannylene-capped cluster [Ni3(dppm)3(μ3-I)(μ3-SnCl2)]+ (2). Clusters 1 and 2 were characterized by 31P NMR, X-ray diffraction, and cyclic voltammetry (CV). Clusters 1 and 2 exhibit single electron redox chemistries, [Ni3(dppm)3(μ3-I)(μ3-SnCl3)]0/•-, [Ni3(dppm)3(μ3-I)(μ3-SnCl2)]+/0, that together comprise a redox equilibrium. Thus, electrochemical reduction of 1 produces first the 49e- cluster radical anion [Ni3(dppm)3(μ3-I)(μ3-SnCl3)]•- which then yields the reduced form of 2, [Ni3(dppm)3(μ3-I)(μ3-SnCl2)], upon chloride dissociation.Keywords
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