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タイトル: | Complexes exhibiting trans(Cl)-RuCl₂(dmso-S)₂ geometry with methyl-picolinate-type neutral N,O-ligands: Synthesis, structural characterization, and chemical behavior analysis in aqueous solutions |
著者: | Toyama, Mari ![]() ![]() ![]() Onishi, Yuto Tanaka, Nobuyoshi Nagao, Noriharu |
キーワード: | Ruthenium(II) complex Hemilabile N, O-ligand 2-picolinic acid methyl ether X-ray crystal structure NMR spectroscopy Absorption spectroscopy |
発行日: | 5-Feb-2025 |
出版者: | Elsevier BV |
誌名: | Journal of Molecular Structure |
巻: | 1321 |
号: | 2 |
論文番号: | 139964 |
抄録: | Methyl picolinate (Mepic) is a starting material in the synthesis of several organic materials and enzymes. Notably, Mepic-ligand-based complexes with metals such as Zn(II), Cd(II), Ru(II), and Rh(III) have garnered attention for catalysis; however, Ru(II)–Mepic complexes remain structurally unexplored. In this study, trans(Cl)-[RuCl₂(dmso-S)₂(Mepic)]·0·25H₂O (1·0·25H₂O, dmso = dimethyl sulfoxide) was produced in a satisfactory yield (80%) via the reaction of trans(Cl)-[RuCl₂(dmso-S)₄] with neutral N,O-ligand Mepic in methanol (MeOH) at room temperature. The use of picolinic acid (Hpic) instead of Mepic in H₂O-ethanol (EtOH) produced the corresponding complex--trans(Cl)-[RuCl₂(dmso-S)₂(Hpic)]·H₂O (2·H₂O)--with a slightly higher yield (82%). Crystal structure analysis of 1·0·25H₂O and 2·H₂O revealed that each chelating ligand coordinated to Ru²⁺ via pyridyl-N and carbonyl-O atoms and Hpic acted as a neutral bidentate ligand in 2. In DMSO, 1 was labile and released Mepic to form [RuCl₂(dmso)₄], owing to the hemilability of N, O-ligand Mepic. In contrast, 2 was inert in DMSO because H⁺ was released from Hpic in solution, forming the anionic mono(pic)Ru complex--trans(Cl)-[RuCl₂(dmso-S)₂(pic-κ²N,O⁻)]⁻. ¹H NMR and UV–Vis spectroscopic studies showed that 2 also generated the anionic mono(pic)Ru complex in aqueous solutions. Although free Mepic is inert in water, 1 underwent thermal hydrolysis in water to produce free MeOH. The dissociation of monodentate ligands was also observed in the thermal hydrolysis of 1. Thus, it was a complicated reaction. The reaction of 1 with equimolar OH⁻ in water quickly and selectively yielded the same complex and a MeOH molecule. Our study will assist in assessing the catalytic potential of this complex and related systems. |
著作権等: | © 2024 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license. |
URI: | http://hdl.handle.net/2433/291777 |
DOI(出版社版): | 10.1016/j.molstruc.2024.139964 |
出現コレクション: | 学術雑誌掲載論文等 |

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