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Synthesis, thermal properties and photoisomerization of trans-[Ru(NO)Py2Cl2(H2O)]H2PO4⋅H2O

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Abstract

The reaction of trans-[Ru(NO)Py 2Cl 2(OH)] with concentrated o-phosphoric acid, after washing the mixture with diethyl ether, gave trans-[Ru(NO)Py 2Cl 2(H 2O)]H 2 PO 4 ⋅2H 3 PO 4 ⋅H 2O (I) in nearly quantitative yield. The structure of this compound was determined by X-ray diffraction analysis: space group P-1. Washing of I with ethanol afforded the dihydrophosphate salt trans-[Ru(NO)Py 2Cl 2(H 2O)]H 2 PO 4 ⋅H 2O (II) (yield 97%). The thermal decomposition of I and II in a helium atmosphere resulted in the formation of ruthenium phosphide RuP as a predominant component along with Ru 2P or RuP 2. Preliminary photoisomerization experiments for trans-[Ru(NO)Py 2Cl 2(OH)] and trans-[Ru(NO)Py 2Cl 2(H 2O)]H 2 PO 4 ⋅H 2O suggested the presence of metastable states. DSC experiments have been carried out for both compounds. The measured kinetic parameters for the metastable decay for trans-[Ru(NO)Py 2Cl 2(H 2O)]H 2 PO 4 ⋅H 2O were E a = 90.7 ± 2.4 kJ/mol, log 10(k 0/sec −1) = 18.9 ±0.6, and T d = 217 K.

Synthesis of trans-[Ru(NO)Py2Cl2(H2O)]H2PO4·H2O and [Ru(NO)Py2Cl2(H2O)]H2PO4·2H3PO4·H2O starting from trans-[Ru(NO)Py2Cl2(OH)] in nearly quantitative yields is reported. Preliminary photoisomerization experiments for trans-[Ru(NO)Py2Cl2(OH)] and trans-[Ru(NO)Py2Cl2(H2O)]H2PO4·H2O complexes have been performed, and metastable states have been detected. Heating of phosphate salts of ruthenium pyridine complexes, as synthesized, afford a mixture of nanoscale ruthenium phosphides.

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Acknowledgements

Authors thank Dr. Gennady A. Kostin and Artem A. Mikhailov for laser experiments; Dr. Anna P. Zubareva, Dr. Olga S. Kosheeva and Dr. Alphiya R. Tsygankova for the elemental analysis; Dr. Dmitry P. Pischur for recording the DSC curves; and Natalya P. Korotkevich for powder X-ray diffraction study.

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Authors and Affiliations

  1. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Akad. Lavrentiev Ave., Novosibirsk, 630090, Russia

    ALEXANDER N MAKHINYA, ILYA V KOROLKOV, MAXIM A IL’IN, IRAIDA A BAIDINA, PAVEL E PLUSNIN, EUGENI A MAXIMOVSKI, ELIZAVETA A BELETSKAYA & NINA I ALFEROVA

  2. Novosibirsk State University, 1 Pirogova Str., Novosibirsk, 630090, Russia

    ALEXANDER N MAKHINYA, ILYA V KOROLKOV, MAXIM A IL’IN, PAVEL E PLUSNIN, EUGENI A MAXIMOVSKI & ELIZAVETA A BELETSKAYA

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  1. ALEXANDER N MAKHINYA
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Correspondence to ALEXANDER N MAKHINYA.

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Supplementary Information (SI)

CCDC No. 1476880 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. DSC curve for trans-[Ru(NO)Py 2Cl 2(OH)], powder diffraction data and microphotographs for thermolysis products of I and II are available in Supplementary Information at www.ias.ac.in/chemsci.

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MAKHINYA, A.N., KOROLKOV, I.V., IL’IN, M.A. et al. Synthesis, thermal properties and photoisomerization of trans-[Ru(NO)Py2Cl2(H2O)]H2PO4⋅H2O. J Chem Sci 129, 441–448 (2017). https://doi.org/10.1007/s12039-017-1261-y

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  • DOI: https://doi.org/10.1007/s12039-017-1261-y

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