The reaction of nitrate ruthenium complex, fac-[RuNO(NH3)2(NO3)3], with pyridine resulted in cis-[RuNO(NH3)2Py2(NO3)](NO3)2·H2O with 84 % yield of the product at room temperature. Addition of any solvent leads to the reaction failure; the excess of pyridine fulfilled the role of a solvent. The DFT simulation of the dissociative mechanism reveals that the nitrate loss from cis-position to NO occurs more easily than for trans-coordinated nitrate. This conclusion is in agreement with the X-ray determined structure of the product. In the solid state, the nitrosyl groups of two neighboring complexes are closely positioned to each other. The small available volume around the nitrosyl group, ca. 0.5 Å3, leads to the enhanced stability of the photoinduced metastable state. The Ru–ON isomer converts back to the ground N-coordinated state with 0.001 s–1 rate constant at 257 K. This O-coordinated isomer of the studied complex is one of the ten known most stable Ru–ON isomers ranked by the “decay” temperature.
|Журнал||Zeitschrift fur Anorganische und Allgemeine Chemie|
|Состояние||Опубликовано - 31 янв 2020|