ILYA V KOROLKOV
Articles written in Journal of Chemical Sciences
Volume 129 Issue 4 April 2017 pp 441-448 Regular Article
The reaction of trans-[Ru(NO)Py₂Cl₂ (OH)] with concentrated o-phosphoric acid, after washing the mixture with diethyl ether, gave trans-[Ru(NO)Py₂Cl₂(H₂O)]H₂PO₄•2H₃PO₄•H₂O (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)Py₂Cl₂ (H₂O)]H₂PO₄•H₂O (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 Ru₂P or RuP₂. Preliminary photoisomerization experiments for trans-[Ru(NO)Py₂Cl₂ (OH)] and trans-[Ru(NO)Py₂Cl₂ (H₂O)]H₂PO₄•H₂O suggested the presenceof metastable states. DSC experiments have been carried out for both compounds. The measured kinetic parameters for the metastable decay for trans-[Ru(NO)Py₂Cl₂ (H₂O)]H₂PO₄•H₂Owere Ea = 90.7± 2.4 kJ/mol, log10(k0/sec−1) = 18.9±0.6, and Td = 217 K.
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