The influence of hydroxide to fluoride substitution in the trans -position to NO on the photochemistry of ruthenium nitrosyl complexes in the solid state and in solution

A new [RuNO(Py) 2 Cl 2 F] (1) complex with a trans NO–Ru–F coordinate was prepared by the reaction of HF and [RuNO(Py) 2 Cl 2 OH] (2). The photochemical properties of [RuNO(Py) 2 Cl 2 X] (X = F, OH) were compared in the solid state and in DMSO solution. In the solid state, blue-light irradiation pro...

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Published inNew journal of chemistry Vol. 47; no. 33; pp. 15506 - 15513
Main Authors Mikhailov, Artem A., Brovko, Anastasiya O., Kuratieva, Nataliya V., Eltsov, Ilia V., Schaniel, Dominik, Kostin, Gennadiy A.
Format Journal Article
LanguageEnglish
Published Cambridge Royal Society of Chemistry 21.08.2023
Royal Society of Chemistry [1987-....]
Subjects
Chemical Sciences
Isomers
Light irradiation
Photochemistry
Ruthenium
Solid state
Substitution reactions
Thermal stability
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Summary:A new [RuNO(Py) 2 Cl 2 F] (1) complex with a trans NO–Ru–F coordinate was prepared by the reaction of HF and [RuNO(Py) 2 Cl 2 OH] (2). The photochemical properties of [RuNO(Py) 2 Cl 2 X] (X = F, OH) were compared in the solid state and in DMSO solution. In the solid state, blue-light irradiation produces isonitrosyl metastable linkage isomers (MS1) in both compounds. For [RuNO(Py) 2 Cl 2 OH], the formation of a side-on coordinated MS2 isomer was also detected after irradiation at 405 nm. The thermal stability of MS1 and MS2 was investigated using DSC, and the corresponding kinetic parameters ( E a and k 0 ) and characteristic decay temperature ( T d ) were determined. The irradiation in DMSO solution results in NO release for both complexes, and the determined quantum yield for 2 is about four times higher compared to that of 1, which also correlates with higher conversion to MS1 and MS2 in the solid state.
ISSN:1144-0546
1369-9261
DOI:10.1039/D3NJ02696E