| Summary: | The reaction of rhenium α-diimine (N-N) tricarbonyl complexes with nitrosonium tetrafluoroborate yields the corresponding dicarbonyl-nitrosyl [Re(CO)<sub>2</sub>(NO)(N-N)X]<sup>+</sup> species (where X = halide). The complexes, accessible in a single step in good yield, are structurally nearly identical higher charge congeners of the tricarbonyl molecules. Substitution chemistry aimed at the realization of equivalent dicationic species (intended for applications as potential antimicrobial agents), revealed that the reactivity of metal ion in [Re(CO)<sub>2</sub>(NO)(N-N)X]<sup>+</sup> is that of a hard Re acid, probably due to the stronger π-acceptor properties of NO<sup>+</sup> as compared to those of CO. The metal ion thus shows great affinity for π-basic ligands, which are consequently difficult to replace by, e.g., σ-donor or weak π-acids like pyridine. Attempts of direct nitrosylation of α-diimine <i>fac</i>-[Re(CO)<sub>3</sub>]<sup>+</sup> complexes bearing π-basic OR-type ligands gave the [Re(CO)<sub>2</sub>(NO)(N-N)(BF<sub>4</sub>)][BF<sub>4</sub>] salt as the only product in good yield, featuring a stable Re-FBF<sub>3</sub> bond. The solid state crystal structure of nearly all molecules presented could be elucidated. A fundamental consequence of the chemistry of [Re(CO)<sub>2</sub>(NO)(N-N)X]<sup>+</sup> complexes, it that the same can be photo-activated towards CO release and represent an entirely new class of photoCORMs.
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