Efficient direct nitrosylation of a-diimine rhenium tricarbonyl complexes to structurally nearly identical higher charge congeners activable towards photo-CO release

Abstract

The reaction of rhenium α-diimine (N-N) tricarbonyl complexes with nitrosonium tetrafluoroborate yields the corresponding dicarbonyl-nitrosyl [Re(CO)2(NO)(N-N)X] + species (where X = halide). The complexes, accessible in a single step in good yied, 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)2(NO)(N-N)X] + is closer to that of a harder Re(III) acid, probably due to the stronger πacceptor properties of NO + 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 week π-acids like pyridine. Attempts of direct nitrosylation of αdiimine fac-[Re(CO)3] + complexes bearing π-basic OR-type ligands gave the [Re(CO)2(NO)(N-N)(BF4)][BF4] salt, as the only product in good yield, featuring a stable Re-F-BF3 bond. The solid state crystal structure of nearly all molecules presented could be elucidated. A fundamental consequence of the chemistry of [Re(CO)2(NO)(N-N)X] + complexes, it that the same can be photo-activated towards CO release and represent an entirely new class of photoCORMs.