Tin-capped trinuclear nickel clusters: redox isomerism between micro(3)-stannyl and micro(3)-stannylene clusters of the class [Ni(3)(dppm)(3)(micro3-I)(micro3-SnCl(x)](n+) (x = 2, n = 1; x = 3, n = 0).
The reaction of Ni(3)(dppm)(3)(micro(3)-I)(2)) with sodium trichlorostannate affords the first tin-capped nickel cluster Ni(3)(dppm)(3)(micro(3)-I)(micro(3)-SnCl(3) (1). A site of coordinative unsaturation at tin can be introduced by the reaction of 1 with Tl[PF(6)] yielding the stannylene-capped cluster [Ni(3)(dppm)(3)(micro(3)-I)(micro(3)-SnCl(2)](+) (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, [Ni(3)(dppm)(3)(micro(3)-I)(micro(3)-SnCl3](0/*-), [Ni(3)(dppm)(3)(micro(3)-I)(micro(3)-SnCl(2)](+/0), that together comprise a redox equilibrium. Thus, electrochemical reduction of 1 produces first the 49e- cluster radical anion [Ni(3)(dppm)(3)(micro(3)-I)(micro(3)-SnCl(3)](*-) which then yields the reduced form of 2, [Ni(3)(dppm)(3)(micro(3)-I)(micro(3)-SnCl(2)], upon chloride dissociation.
Department of Chemistry and Biochemistry, University of California at San Diego, 9500 Gilman Drive, La Jolla, California 92093-0358, USA.
Brian K
BK
Breedlove
Philip E
PE
Fanwick
Clifford P
CP
Kubiak