Efficient Direct Nitrosylation of α-Diimine Rhenium Tricarbonyl Complexes to Structurally Nearly Identical Higher Charge Congeners Activable towards Photo-CO Release

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 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)2(NO)(N-N)X]+ is that of a hard Re acid, probably due to the stronger π-acceptor 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 weak π-acids like pyridine. Attempts of direct nitrosylation of α-diimine 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-FBF3 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.

The role of zero-field splitting and π-stacking interaction of different nitrogen-donor ligands on the optical properties of luminescent rhenium tricarbonyl complexes

Rhenium tricarbonyl complexes are one of the most important classes of coordination compounds in inorganic chemistry. Exploring their luminescent excited states, lowest singlet (S1), and the lowest triplet (T1), is...

Flexible to rigid: IR spectroscopic investigation of a rhenium-tricarbonyl-complex at a buried interface

Immobilized rhenium tricarbonyl complexes were embedded in ALD deposited ZrO2, and investigated by (time resolved) infrared spectroscopy. The initially solvent exposed molecules react on the change of their environment.

Photochemistry of P,N-bidentate rhenium(i) tricarbonyl complexes: reactive species generation and potential application for antibacterial photodynamic therapy

Three P,N-rhenium tricarbonyl complexes exhibited photoisomerization upon irradiation at 365 nm, and no CO release was detected. The antibacterial activity is attributed to their singlet oxygen generation, following the same decreasing order: RePNBr > RePNTfO > RePNNBr.

Substitution reactivity and structural variability induced by tryptamine on the biomimetic rhenium tricarbonyl complex

The biomimetic tryptamine rhenium tricarbonyl complex shows rapid substitution reactivity on the 6th position as well as cytotoxicity and photoluminescence capability induced by the salicylidene bidentate ligand.