Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Synthesis of the Ruthenium Nitrosyl Complex with Coordinated Ammonia and Pyridine at Room Temperature. / Vorobyev, Vasily; Kostin, Gennadiy A.; Baidina, Iraida A. и др.
в: Zeitschrift fur Anorganische und Allgemeine Chemie, Том 646, № 2, 31.01.2020, стр. 58-64.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Synthesis of the Ruthenium Nitrosyl Complex with Coordinated Ammonia and Pyridine at Room Temperature
AU - Vorobyev, Vasily
AU - Kostin, Gennadiy A.
AU - Baidina, Iraida A.
AU - Mikhailov, Artem A.
AU - Korolkov, Ilya V.
AU - Emelyanov, Vyacheslav A.
N1 - Publisher Copyright: © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Copyright: Copyright 2020 Elsevier B.V., All rights reserved.
PY - 2020/1/31
Y1 - 2020/1/31
N2 - 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.
AB - 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.
KW - Ammine
KW - Metastable state
KW - Nitrosyl
KW - Pyridine
KW - Ruthenium
KW - STORAGE
KW - NO
KW - OXIDE
KW - RU
KW - NITRIC-ACID SOLUTIONS
KW - CRYSTAL-STRUCTURE
KW - NITROSATION
KW - INDUCED METASTABLE STATES
KW - DELIVERY
KW - OXYGEN
UR - http://www.scopus.com/inward/record.url?scp=85078764105&partnerID=8YFLogxK
U2 - 10.1002/zaac.201900246
DO - 10.1002/zaac.201900246
M3 - Article
AN - SCOPUS:85078764105
VL - 646
SP - 58
EP - 64
JO - Zeitschrift fur Anorganische und Allgemeine Chemie
JF - Zeitschrift fur Anorganische und Allgemeine Chemie
SN - 0044-2313
IS - 2
ER -
ID: 23327727