Synthesis, some properties, and crystalline modifications of fac-[Ru(NO)(Py)₂Cl₃]

详细信息    查看全文

• 作者：A. N. Makhinya ; M. A. Il’in…
• 关键词：ruthenium nitrosyl ; amino complexes ; chloro complexes ; pyridine ; X ; ray diffraction analysis ; 1H NMR spectroscopy ; IR spectroscopy ; thermogravimetry ; photoisomerization ; differential scanning calorimetry
• 刊名：Russian Journal of Coordination Chemistry
• 出版年：2016
• 出版时间：December 2016
• 年：2016
• 卷：42
• 期：12
• 页码：768-774
• 全文大小：
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Physical Chemistry; Inorganic Chemistry;
• 出版者：Pleiades Publishing
• ISSN：1608-3318
• 卷排序：42

文摘

According to the data of 1H NMR spectroscopy, trans-hydroxochloro complexes containing from two to four pyridine molecules in the internal sphere are formed on the heating of a dilute aqueous solution of K₂[Ru(NO)Cl₅] with pyridine. The evaporation of the reaction solution with concentrated hydrochloric acid gives fac-[Ru(NO)(Py)₂Cl₃] (I) in a yield of ~90%. The structures of two crystalline modifications of this complex are determined by X-ray diffraction analysis (CIF files ССDС nos. 1452208 (Ia) and 1452207 (Ib)). IR spectroscopy shows that the irradiation of complex I (λ ~ 450 nm, T = 80 K) results in photoisomerization with the formation of the metastable state MS1 in which the nitroso group is coordinated by the oxygen atom. The activation parameters of the photoisomerization are determined from the data of differential scanning calorimetry (DSC). Compound trans-[Ru(NO)Py₄(OH)]Cl₂ ∙ H₂O is isolated in a yield of ~70% on reflux of complex I with a pyridine excess in an aqueous solution, and the presence of molecules of water of crystallization in this compound is confirmed by thermal gravimetry (TG) and IR spectroscopy.