cis-[Ru(NO)(NO2)(pyridine-2-carboxylate)] | 170966-89-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: cis-[Ru(NO)(NO2)(pyridine-2-carboxylate)]
• 英文别名: cis-[Ru(NO)(ONO)(pyridine-2-carboxylate)]
• CAS: 170966-89-9
• 化学式: C₁₂H₈N₄O₇Ru
• 分子量: 421.288
• InChiKey: YGIBIQSXUSHAAV-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  高氯酸 、 cis-[Ru(NO)(NO2)(pyridine-2-carboxylate)] 、 sodium perchlorate 、 水 以 高氯酸 为溶剂， 以59%的产率得到[Ru(NO)(H2O)(pyridine-2-carboxylate)]ClO4
  参考文献：
  名称：

  Redox- and Thermally-Induced Nitro-Nitrito Linkage Isomerizations of Ruthenium(II) Complexes Having Nitrosyl as a Spectator Ligand

  摘要：

  Three new nitro-nitrito isomeric pairs are prepared and characterized as cis-[Ru(NO)X(2,2'-bpy)(2)](2+), Cis-[Ru-(NO)X(ppca)(2)], and cis-[Ru(NO)X(2,2'-bpy)(py)(2)](2+) (X = ONO, NO2; 2,2'-bpy = 2,2'-bipyridine; pyca = pyridine-2-carboxylate; py = pyridine). Molecular structures of the isomers are established by X-ray structure studies, except for cis-[Ru(NO)(ONO) (pyca)(2)]. Redox-induced linkage isomerization occurs in cis-[Ru(NO)X(2,2'-bpy)-py)(2)](2+) (X = ONO, NO2); the nitrito isomer is capable of being interchanged to the nitro isomer, via a one-electron redox process of the (RuNO)(3+) moiety. Thermally-induced isomerization also occurs, with different isomerization patterns, depending on the spectator ligands: cis-[Ru(NO)X(2,2'-bpy)(2)](2+) gave an equilibrium mixture of the nitro and the nitrito isomers; in cis-[Ru(NO)X(pyca)(2)], the nitrito isomer changed to the nitro isomer; contrastively, the nitro isomer of cis-[Ru(NO)X(2,2'-bpy) (py)(2)](2+) converted to the nitrito isomer. Some mechanistic investigations about the isomerization reactions were carried out using various N-15-substituted complexes; no oxygen exchange reaction between the nitrosyl and the nitro (nitrito) ligands was found.

  DOI：

  10.1021/ic00128a013
• 作为产物：
  描述：

  sodium nitrite 、 cis-chloronitrosylbis(pyridine-2-carboxylato)ruthenium 以 乙醇 、 水 为溶剂， 以68%的产率得到cis-[Ru(NO)(NO2)(pyridine-2-carboxylate)]
  参考文献：
  名称：

  Redox- and Thermally-Induced Nitro-Nitrito Linkage Isomerizations of Ruthenium(II) Complexes Having Nitrosyl as a Spectator Ligand

  摘要：

  Three new nitro-nitrito isomeric pairs are prepared and characterized as cis-[Ru(NO)X(2,2'-bpy)(2)](2+), Cis-[Ru-(NO)X(ppca)(2)], and cis-[Ru(NO)X(2,2'-bpy)(py)(2)](2+) (X = ONO, NO2; 2,2'-bpy = 2,2'-bipyridine; pyca = pyridine-2-carboxylate; py = pyridine). Molecular structures of the isomers are established by X-ray structure studies, except for cis-[Ru(NO)(ONO) (pyca)(2)]. Redox-induced linkage isomerization occurs in cis-[Ru(NO)X(2,2'-bpy)-py)(2)](2+) (X = ONO, NO2); the nitrito isomer is capable of being interchanged to the nitro isomer, via a one-electron redox process of the (RuNO)(3+) moiety. Thermally-induced isomerization also occurs, with different isomerization patterns, depending on the spectator ligands: cis-[Ru(NO)X(2,2'-bpy)(2)](2+) gave an equilibrium mixture of the nitro and the nitrito isomers; in cis-[Ru(NO)X(pyca)(2)], the nitrito isomer changed to the nitro isomer; contrastively, the nitro isomer of cis-[Ru(NO)X(2,2'-bpy) (py)(2)](2+) converted to the nitrito isomer. Some mechanistic investigations about the isomerization reactions were carried out using various N-15-substituted complexes; no oxygen exchange reaction between the nitrosyl and the nitro (nitrito) ligands was found.

  DOI：

  10.1021/ic00128a013

文献信息

• Regulation of Geometry around the Ruthenium Center of Bis(2-pyridinecarboxylato) Complexes by the Nitrosyl Moiety:  Syntheses, Structures, and Theoretical Studies
  作者：Toshiyuki Hirano、Takao Oi、Hirotaka Nagao、Keiji Morokuma

  DOI：10.1021/ic0344261

  日期：2003.10.1

  cis-[Ru(NO)Cl(pyca)(2)] (pyca = 2-pyridinecarboxylato), in which the two pyridyl nitrogen atoms of the two pyca ligands coordinate at the trans position to each other and the two carboxylic oxygen atoms at the trans position to the nitrosyl ligand and the chloro ligand, respectively (type I shown as in Chart 1), reacted with NaOCH3 to generate cis-[Ru(NO)(OCH3)(pyca)(2)] (type I). The geometry of this complex was confirmed to be the same as the starting complex by X-ray crystallography: C13.5H13N3O6.5Ru; monoclinic, P2(1)/n; a = 8.120(1), b = 16.650(1), c = 11.510(1) Angstrom; beta = 99.07(1)degrees; V = 1536.7(2) Angstrom(3); Z = 4. The cis-trans geometrical change reaction occurred in the reactions of cis-[Ru(NO)(OCH3)(pyca)(2)] (type I) in water and alcohol (ROH, R = CH3, C2H5) to form [trans-Ru-(NO)(pyca)(2)}(2)(H3O2)](+) (type V) and trans-[Ru(NO)(OR)(pyca)(2)] (type V). The reactions of the trans-form complexes, trans-[Ru(NO)(H2O)(pyca)(2)](+) (type V) and trans-[Ru(NO)(OCH3)(pyca)(2)] (type V), with Cl- in hydrochloric acid solution afforded the cis-form complex, cis-[Ru(NO)Cl(pyca)(2)] (type I). The favorable geometry of [Ru(NO)X(pyca)(2)](n+) depended on the nature of the coexisting ligand X. This conclusion was confirmed by theoretical, synthetic, and structural studies. The mono-pyca-containing nitrosylruthenium complex (C2H5)(4)N[Ru(NO)Cl(3)pyca)] was synthesized by the reaction of [Ru(NO)Cl-5](2-) with Hpyca and characterized by X-ray structural analysis: C14H24N3O3Cl3Ru; triclinic, P (1) over bar, a = 7.631 (1), b = 9.669(1), c = 13.627(1) Angstrom; alpha = 83.05(2), beta = 82.23(1), gamma = 81.94(1)degrees; V = 981.1(1) Angstrom(3); Z = 2. The type II complex of cis-[Ru(NO)Cl(pyca)(2)] was synthesized by the reaction of [Ru(NO)Cl-3(pyca)(2)](-) or [Ru(NO)CI5]2- with Hpyca and isolated by column chromatography. The structure was determined by X-ray structural analysis: C12H8N3O5ClRu; monoclinic, P2(1)/n; a = 10.010(1), b = 13.280(1), c = 11.335(1) Angstrom; beta = 113.45(1)degrees; V = 1382.4(2) Angstrom(3); Z = 4.