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Synthesis of the Ruthenium Nitrosyl Complex with Coordinated Ammonia and Pyridine at Room Temperature
Author(s) -
Vorobyev Vasily,
Kostin Gennadiy A.,
Baidina Iraida A.,
Mikhailov Artem A.,
Korolkov Ilya V.,
Emelyanov Vyacheslav A.
Publication year - 2020
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201900246
Subject(s) - pyridine , chemistry , ruthenium , solvent , metastability , yield (engineering) , ammonia , photochemistry , medicinal chemistry , catalysis , organic chemistry , materials science , metallurgy
The reaction of nitrate ruthenium complex, fac ‐[RuNO(NH 3 ) 2 (NO 3 ) 3 ], with pyridine resulted in cis ‐[RuNO(NH 3 ) 2 Py 2 (NO 3 )](NO 3 ) 2 · H 2 O 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 Å 3 , 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.