Tin-capped trinuclear nickel clusters: Redox isomerism between mu(3)-stannyl and mu(3)-stannylene clusters of the class [Ni-3(dppm)(3)(mu(3)-l)(mu(3)-SnClx)](n+) (x=2, n=1; x=3, n=0)

Breedlove BK; Fanwick PE; Kubiak CP

Inorganic Chemistry, Vol.41, No.17, 4306-4308, 2002

DOI10.1021/ic020108a Export Citation

Tin-capped trinuclear nickel clusters: Redox isomerism between mu(3)-stannyl and mu(3)-stannylene clusters of the class [Ni-3(dppm)(3)(mu(3)-l)(mu(3)-SnClx)](n+) (x=2, n=1; x=3, n=0)

Breedlove BK, Fanwick PE, Kubiak CP

The reaction of Ni-3(dppm)(3)(mu(3)-1)(2) with sodium trichlorostannate affords the first tin-capped nickel cluster Ni-3(dppm)(3)(mu(3)-1)(mu(3)-SnCl3) (1). A site of coordinative unsaturation at tin can be introduced by the reaction of 1 with T1[PF6] yielding the stannylene-capped cluster [Ni-3(dppm)(3)(mu(3)-1)(mu(3)-SnCl2)](+) (2). Clusters 1 and 2 were characterized by P-31 NMR, X-ray diffraction, and cyclic voltammetry (CV). Clusters 1 and 2 exhibit single electron redox chemistries, [Ni-3(dppm)(3)(mu(3)-1)(mu(3)-SnCl3)](0/.-) , [Ni-3(dppm)(3)(mu(3)-1)(mu(3)-SnCl3)](+/0), that together comprise a redox equilibrium. Thus, electrochemical reduction of 1 produces first the 49e(-) cluster radical anion [Ni-3(dppm)(3)(mu(3)-1)(mu(3)-SnCl3)](.-) which then yields the reduced form of 2, [Ni-3(dppm)(3)(mu(3)-1)(mu(3)-SnCl2)], upon chloride dissociation.