A New Heteroleptic Complex of Nitrosyl Ruthenium with Ethylenediamine and the NO–Ru–F Trans-Coordinate: Synthesis, Structure, and Photoinduced Linkage Isomerization

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A New Heteroleptic Complex of Nitrosyl Ruthenium with Ethylenediamine and the NO–Ru–F Trans-Coordinate: Synthesis, Structure, and Photoinduced Linkage Isomerization. / Brovko, A. O.; Kuratieva, N. V.; Emelyanov, V. A. et al.

In: Journal of Structural Chemistry, Vol. 65, No. 7, 07.2024, p. 1404-1411.

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

BibTeX

@article{d720c949b8f144b4a9093a49ce88132f,

title = "A New Heteroleptic Complex of Nitrosyl Ruthenium with Ethylenediamine and the NO–Ru–F Trans-Coordinate: Synthesis, Structure, and Photoinduced Linkage Isomerization",

abstract = "A new method is proposed to synthesize ethylenediamine complex [RuNO(en)2OH]I2 from K2[RuNOCl5], which increases the target product yield to 76%. Subsequent treatment of nitrate salt [RuNO(en)2 OH](NO3)2 with concentrated HF with the precipitation of HClO4 gives [RuNO(en)2F](ClO4)2 with a quantitative yield. According to the single crystal XRD data, in the [RuNO(en)2F]2+ cationic moiety, nitrosyl and fluoride are in the trans-position relative to each other, and in the ruthenium coordination environment, the equatorial plane is composed of four nitrogen atoms from ethylenediamine ligands. The 450 nm light irradiation of the [RuNO(en)2F](ClO4)2 complex at 80 K results in the formation of metastable linkage isomer MS1 with nitrosyl group coordination through the oxygen atom. According to the IR spectroscopic data, the population of MS1 is about 1%, and the respective vibrational band disappears when heated in a temperature range of 280-310 K. The activation parameters of the MS1–GS (ground state) transition according to the DSC data are Ea = 107.1±6.8 kJ/mol, lnk0 = 36.1±2.6.",

keywords = "decomposition temperature, ethylenediamine, linkage isomerism, metastable states, nitrosyl complexes, photoisomerization, ruthenium, single crystal X-ray diffraction",

author = "Brovko, {A. O.} and Kuratieva, {N. V.} and Emelyanov, {V. A.} and Pishchur, {D. P.} and Kostin, {G. A.}",

note = "The authors are grateful to the Russian Science Foundation for the financial support of the research (project 22-43-09001).",

year = "2024",

month = jul,

doi = "10.1134/S0022476624070114",

language = "English",

volume = "65",

pages = "1404--1411",

journal = "Journal of Structural Chemistry",

issn = "0022-4766",

publisher = "Springer GmbH & Co, Auslieferungs-Gesellschaf",

number = "7",

}

RIS

TY - JOUR

T1 - A New Heteroleptic Complex of Nitrosyl Ruthenium with Ethylenediamine and the NO–Ru–F Trans-Coordinate: Synthesis, Structure, and Photoinduced Linkage Isomerization

AU - Brovko, A. O.

AU - Kuratieva, N. V.

AU - Emelyanov, V. A.

AU - Pishchur, D. P.

AU - Kostin, G. A.

N1 - The authors are grateful to the Russian Science Foundation for the financial support of the research (project 22-43-09001).

PY - 2024/7

Y1 - 2024/7

N2 - A new method is proposed to synthesize ethylenediamine complex [RuNO(en)2OH]I2 from K2[RuNOCl5], which increases the target product yield to 76%. Subsequent treatment of nitrate salt [RuNO(en)2 OH](NO3)2 with concentrated HF with the precipitation of HClO4 gives [RuNO(en)2F](ClO4)2 with a quantitative yield. According to the single crystal XRD data, in the [RuNO(en)2F]2+ cationic moiety, nitrosyl and fluoride are in the trans-position relative to each other, and in the ruthenium coordination environment, the equatorial plane is composed of four nitrogen atoms from ethylenediamine ligands. The 450 nm light irradiation of the [RuNO(en)2F](ClO4)2 complex at 80 K results in the formation of metastable linkage isomer MS1 with nitrosyl group coordination through the oxygen atom. According to the IR spectroscopic data, the population of MS1 is about 1%, and the respective vibrational band disappears when heated in a temperature range of 280-310 K. The activation parameters of the MS1–GS (ground state) transition according to the DSC data are Ea = 107.1±6.8 kJ/mol, lnk0 = 36.1±2.6.

AB - A new method is proposed to synthesize ethylenediamine complex [RuNO(en)2OH]I2 from K2[RuNOCl5], which increases the target product yield to 76%. Subsequent treatment of nitrate salt [RuNO(en)2 OH](NO3)2 with concentrated HF with the precipitation of HClO4 gives [RuNO(en)2F](ClO4)2 with a quantitative yield. According to the single crystal XRD data, in the [RuNO(en)2F]2+ cationic moiety, nitrosyl and fluoride are in the trans-position relative to each other, and in the ruthenium coordination environment, the equatorial plane is composed of four nitrogen atoms from ethylenediamine ligands. The 450 nm light irradiation of the [RuNO(en)2F](ClO4)2 complex at 80 K results in the formation of metastable linkage isomer MS1 with nitrosyl group coordination through the oxygen atom. According to the IR spectroscopic data, the population of MS1 is about 1%, and the respective vibrational band disappears when heated in a temperature range of 280-310 K. The activation parameters of the MS1–GS (ground state) transition according to the DSC data are Ea = 107.1±6.8 kJ/mol, lnk0 = 36.1±2.6.

KW - decomposition temperature

KW - ethylenediamine

KW - linkage isomerism

KW - metastable states

KW - nitrosyl complexes

KW - photoisomerization

KW - ruthenium

KW - single crystal X-ray diffraction

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85199809624&origin=inward&txGid=3b73cfb2918f01898e4557ba4d8203ee

UR - https://www.mendeley.com/catalogue/7737351f-d9d7-3ee5-a74d-2bab7d28a65e/

U2 - 10.1134/S0022476624070114

DO - 10.1134/S0022476624070114

M3 - Article

VL - 65

SP - 1404

EP - 1411

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 7

ER -

ID: 60862754