Abstract
Interesting reactivity was observed in reactions of SO2 with [Zn(Cp*)2] and [(Cp*)ZnI-ZnI(Cp*)]. These reactions proceeded with insertion of SO2 into the Zn-C bonds. Spectacularly, the lability of the C-S bond in the O2SCp* ligands led to the thermal decomposition of [Zn(O2SCp*)2(tmeda)] to afford [Zn2(μ-SO3)(μ-S2O4)(tmeda)2].
Highlights
Showcasing research from the laboratory of Dr Peter Roesky, Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany
We report the reactions between SO2 and the zinc complexes, [Zn(Cp*)2] and [(Cp*)ZnI–ZnI(Cp*)] (Cp* = C5Me5À)
When two equivalents of SO2 were condensed onto a stirring solution of [Zn(Cp*)2] in thf, a white solid precipitated immediately
Summary
When [(Cp*)ZnI–ZnI(Cp*)] was treated with SO2, complete oxidation of ZnI to ZnII was observed, and the zinc oxo-cluster, [Zn4(O2SCp*)6O] (2), was obtained in moderate yield (Scheme 1). From insertion of SO2 into the Zn–Cp* bonds, analogously to 1, and possibly reduction of SO2 or an in situ formed derivative by the Zn–Zn bond to abstract an oxygen atom, but other pathways cannot be ruled out.[8] We do not think that water is a likely source of the oxide ion since we used high purity SO2 and complex 2 was isolated multiple times from different batches of [(Cp*)ZnI–ZnI(Cp*)].9 we did not ever observe the formation of Zn metal, which would accompany disproportionation, and we believe that the Zn–Zn unit is oxidised by SO2 or an in situ formed derivative, e.g. the O2SCp* ligands.
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