Synthesis of the Ruthenium Nitrosyl Complex with Coordinated Ammonia and Pyridine at Room Temperature

Vasily Vorobyev; Gennadiy A. Kostin; Iraida A. Baidina; Artem A. Mikhailov; Ilya V. Korolkov; Vyacheslav A. Emelyanov

doi:10.1002/zaac.201900246

Synthesis of the Ruthenium Nitrosyl Complex with Coordinated Ammonia and Pyridine at Room Temperature

Vasily Vorobyev, Gennadiy A. Kostin, Iraida A. Baidina, Artem A. Mikhailov, Ilya V. Korolkov, Vyacheslav A. Emelyanov

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	58-64
Number of pages	7
Journal	Zeitschrift fur Anorganische und Allgemeine Chemie
Volume	646
Issue number	2
DOIs	https://doi.org/10.1002/zaac.201900246
Publication status	Published - 31 Jan 2020

Keywords

Ammine
Metastable state
Nitrosyl
Pyridine
Ruthenium
STORAGE
NO
OXIDE
RU
NITRIC-ACID SOLUTIONS
CRYSTAL-STRUCTURE
NITROSATION
INDUCED METASTABLE STATES
DELIVERY
OXYGEN

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title = "Synthesis of the Ruthenium Nitrosyl Complex with Coordinated Ammonia and Pyridine at Room Temperature",

abstract = "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 {\AA}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.",

keywords = "Ammine, Metastable state, Nitrosyl, Pyridine, Ruthenium, STORAGE, NO, OXIDE, RU, NITRIC-ACID SOLUTIONS, CRYSTAL-STRUCTURE, NITROSATION, INDUCED METASTABLE STATES, DELIVERY, OXYGEN",

author = "Vasily Vorobyev and Kostin, {Gennadiy A.} and Baidina, {Iraida A.} and Mikhailov, {Artem A.} and Korolkov, {Ilya V.} and Emelyanov, {Vyacheslav A.}",

year = "2020",

month = jan,

day = "31",

doi = "10.1002/zaac.201900246",

language = "English",

volume = "646",

pages = "58--64",

journal = "Zeitschrift fur Anorganische und Allgemeine Chemie",

issn = "0044-2313",

publisher = "Wiley-VCH Verlag",

number = "2",

}

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.

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 -

Synthesis of the Ruthenium Nitrosyl Complex with Coordinated Ammonia and Pyridine at Room Temperature

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