With the isolation and characterization of the first ZnI compound [Zn2Cp*2] (Cp* = Pentamethylcyclopentadienyl) Carmona et al. succeeded to set a milestone in organometallic chemistry. Rapidly, a number of publications originated from this work focusing on the elucidation of the ZnI-ZnI bonding situation and its reactivity. Despite the ever-growing interest in low valent zinc compounds the insight into cationic derivatives is rather limited. However, the selective removal of the protecting Cp* ligands from [Zn2Cp*2] is feasible leading to the [Hg2]2+ analogon [Zn2]2+, if an adequately stabilizing ligand environment is provided. In this poster we will present a straightforward, reliable synthetic pathway to novel cationic low valent zinc species via selective cleavage of Zn-Cp* bonds in [Zn2Cp*2]. Treatment of Carmona's reagent with [FeCp2][BAr4F] leads to a rather unusual oxidation of the [Cp*]- ligands giving access to the unaffected ZnI-ZnI unit, which can be isolated in form of its THF adduct [Zn2(THF)6][BAr4F]2 (BAr4F = B{C6H3(CF3)2}4) (1  ). The substitution of the coordinating solvent molecules in this virtually naked [Zn2]2+ dication by main group donor ligands such as phosphines or guanidinates and electron rich transition metal complexes like [M(GaCp*)4] (M = Pd, Pt) will be discussed. A key example is the reaction of 1  with [GaCp*] to give [Zn2(GaCp*)6][BAr4F]2, a novel main group metal Zn/Ga cluster. Following this principle a broad spectrum of such substitution reactions will be presented and discussed. 

Oxidative cleavage of Zn-Cp* bonds: [Zn<sub>2</sub>]<sup>2+</sup> as a building block for novel low valent zinc compounds

246th National Meeting (2013)

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Oxidative cleavage of Zn-Cp* bonds: [Zn2]2+ as a building block for novel low valent zinc compounds

Oxidative cleavage of Zn-Cp* bonds: [Zn₂]²⁺ as a building block for novel low valent zinc compounds