Stable dicationic dioxoliums and fate of their dioxolyl radicals

International audienceStable dicationic dioxolium salts featuring an ancillary vinamidinium pattern were synthesized and characterized. Although highly reactive, they were found otherwise easy to handle under inert atmosphere. This offered the opportunity to generate and study the fate of unknown 1,3-dioxolyl radicals. Depending on substituents, reduction led to the formation of dimers of either dioxolyl or cyclohexadienyl radicals, stemming from a process that is related to the Surzur-Tanner rearrangement. The cyclohexadienyl radical could be characterized in the case of a tri(tert-butyl)phenyl group, which prevents dimerization processes

Complexation to [Ru(bpy)2]2+: the trick to functionalize 3,3′-disubstituted-2,2′-bipyridine

International audienceWhile many papers reported the synthesis and chemical transformations of x,x′-disubstituted-2,2′-bipyridine with x = 4, 5 or 6, this is not the case when x = 3. Though, such 3,3′-disubstituted-2,2′-bipyridines would be a useful building block for the design of new original complexes. Here we report the results of our investigation concerning the synthesis of members of this family. This study led to the formation of several [(2,2′-bipyridine)2Ru(3,3′-dialkylated-2,2′-bipyridine)]2+ complexes highlighting a surprising chemical behaviour of the 3,3′-disubstituted-2,2′-bipyridine ligand compared to its 4,4′, 5,5′ and 6,6′-homologues

Ligand assisted cleavage of uranium oxo-clusters

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