Sandwich complexes are important building blocks in medicinal inorganic chemistry for group 6 and 8 elements but are almost unknown for the manganese triad. We present the syntheses and full characterization of the mixed-arene Tc sandwich complexes [Tc(η-hmbz)(η-CH-NH)](PF) and [Tc(η-hmbz)(η-CH-Br)](PF). Both comprise functionalities for conjugation to targeting molecules or for being included as substructures in pharmaceutically active lead compounds. Since η-benzene ligands are too stably bound to be replaced with incoming ligands, we prepared naphthalene complexes [Re(η-CH)(η-napht)] and [Re(η-napht)]. Their reactivities towards substitution are increased and one or both naphthalene ligands can be replaced with mono- or multi-dentate ligands. Combining the features of Tc and Re may lead to a molecule-based theranostic approach.

A methodology for the synthesis of oligophosphate conjugates using phosphordiamidites is described. This strategy facilitates the straightforward preparation of C2-symmetric dinucleoside tri-, penta-, and heptaphosphates. Moreover, unsymmetric compounds such as thiamine adenosine triphosphate and thiamine cytidine triphosphate can be prepared. The material is used to study the inhibitory activity of thiaminylated nucleotides against adenosine diphosphate ribosyltransferases.

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