tris(2,2'-bipyridine)osmium(III)(3+) | 30032-51-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: tris(2,2'-bipyridine)osmium(III)(3+)
• 英文别名: [osmium(III)(2,2'-bipyridine)3](3+)；tris(2,2'-bipyridine)osmium(III)；[Os(III)(2,2'-bipyridine)3](3+)；[Os(2,2'-bipyridine)3](3+)；{Os(bpy)3}(3+)；[osmium(III)(2,2’-bipyridyl)₃](3+)；Δ-[Os(2,2'-bipyridine)3](3+)
• CAS: 30032-51-0；24191-06-8
• 化学式: C₃₀H₂₄N₆Os
• 分子量: 658.761
• InChiKey: SUFCLUADQWULTA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  tris(2,2'-bipyridine)osmium(III)(3+) 以 水 为溶剂， 以90%的产率得到三(2,2'-联吡啶)锇(2+)
  参考文献：
  名称：

  Instability of the oxidation catalysts [OsIII(tpy)(bpy)(py)]3+ and [OsIII(bpy)3]3+ in alkaline solution

  摘要：

  The Os(III) complexes [Os-III(tpy)(bpy)(py)](3+) and [Os-III(bpy)(3)](3+) (bpy: 2,2'-bipyridine, py: pyridine, tpy: 2,2',2"-terpyridine) are unstable toward self-reduction in alkaline solution. Product analysis performed by using UV-Vis spectroscopy, cyclic voltammetry, HPLC and GC show that ca. 90% of the reduced product that appears is the unmodified polypyridyl complex of Os(II), [Os-II(tpy)(bpy)(py)](2+) or [Os-II(bpy)(3)](2+). The remaining 10% of the products are accounted for by other Os(II) complexes, including several which appear to have undergone varying degrees of ligand oxidation or substitution. Another product of the reduction of [Os-III(tpy)(bpy)(py)](3+) in basic solution has been identified as [Os-II(tpy)(bpy)(OH2)](2+) which results from metal reduction and concomitant pyridine ligand loss. No O-2 was detected as a product of the base-catalyzed self-reduction reaction. The Os(III) complexes are stable towards self-reduction and ligand loss in the dark in acetonitrile or aqueous solutions buffered below pH = 6. The rates observed for the self-reduction processes are sufficiently rapid at pH values above 7 that useful catalytic rate data cannot be obtained in basic solution unless the substrate of interest is sufficiently reactive and is present in large excess. Triple mixing, pH jump techniques have successfully been employed to observe reaction rates under strongly alkaline conditions. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2003.11.001
• 作为产物：
  描述：

  三(2,2'-联吡啶)锇(2+) 在 Br₂^(1-) or (SCN)2^(1-) or N₃ 作用下， 以 水 为溶剂， 生成 tris(2,2'-bipyridine)osmium(III)(3+)
  参考文献：
  名称：

  Faraggi, M.; Klapper, M.H., Journal de Chimie Physique et de Physico-Chimie Biologique, 1993, vol. 90, # 4, p. 711 - 744

  摘要：

  DOI：

文献信息

• Analysis of Electrolysis Reactions of Metal Complexes Using On-Line Electrospray Ionization Mass Spectrometry with a Compact Electrolytic Flow-Through Cell
  作者：Ryuichi Arakawa、Tsutomu Abura、Tsuyoshi Fukuo、Hironobu Horiguchi、Gen-etsu Matsubayashi

  DOI：10.1246/bcsj.72.1519

  日期：1999.7

  electrolysis of [Ru(bpy)2(en)](ClO4)2 (en = ethylenediamine) formed two complex products along with the elimination of two and four hydrogen atoms from the en ligand. The structure of the two complex products was determined to be a monoimine and diimine complex, based on an electrolysis experiment using a deuterium-labeled complex, [Ru(bpy)2(ed)](ClO4)2 (ed = ethylene-d4-diamine, H2N–CD2–CD2–NH2). The

  通过在电喷雾针上游安装紧凑、高效的流通池，开发了用于电解反应的在线电喷雾电离质谱分析。电极的设计是为了避免电解过程中形成的氧化产物的任何减少。进行了 Ru 和 Os 金属络合物的电解氧化反应以检查系统的性能。通过电解 [M(bpy)3](PF6)2（其中 M = Ru 和 Os，bpy = 2,2'-联吡啶），我们检测到单电子氧化产物 [M(bpy)3]3 +。[Ru(bpy)2(en)](ClO4)2（en = 乙二胺）的电解形成了两种复杂的产物，同时从 en 配体中消除了两个和四个氢原子。两种复合产物的结构被确定为单亚胺和二亚胺复合物，基于使用氘标记复合物的电解实验，[Ru(bpy)2(ed)]( )2（ed = 乙烯-d4-二胺，H2N-CD2-CD2-NH2）。结果表明，电...
• The oxidation of ascorbic acid by tris(2,2′-bipyridine) complexes of osmium(III), ruthenium(III) and nickel(III) in aqueous media: Applications of the Marcus cross-relation
  作者：Donal H. Macartney、Norman Sutin

  DOI：10.1016/s0020-1693(00)81430-9

  日期：1983.1

  oxidation of L-ascorbic acid (H2A) by tris(2,2′-bypyridine) and tris-(4,4′-dimethyl-2,2′-bipyridine) complexes of osmium(III), ruthenium(III), and nickel(III) have been investigated in acidic aqueous media at 9–25 °C. The observed inverse acid dependence, -d[ML3+3]/dt = 2(k1 + k2K1/[H+])(ML3+3][H2A], suggest a mechanism involving H2A and HA− pathways, for which the specific rate and activation parameters

  s（3,2,2'-bypyridine）和tris-（4,4'-dimethyl-2,2'-bipyridine）配合物对L-抗坏血酸（H 2 A）外球氧化的动力学III），钌（III）和镍（III）已在9–25°C的酸性水性介质中进行了研究。观察到的反酸依赖性-d [ML 3+ 3 ] / dt = 2（k 1 + k 2 K 1 / [H + ]）（ML 3+ 3 ] [H 2 A]，表明涉及H 2的机理A和HA -已经确定了具体速率和激活参数的途径。这些和以前报道的涉及抗坏血酸物质的交叉反应速率常数在马库斯关系方面是相关的。单电子对的自交换参数的估计：H 2 A / H 2 A + ·，k 11 = 2×10 3 M - s -1 ; HA - / HA·，K 11 = 1×10 5 中号-小号-1 ; A 2- / A-·，k 11 = 2×10 5 M - s -1，根据由质子和
• Mechanistic Implications of Proton Transfer Coupled to Electron Transfer
  作者：Estelle L. Lebeau、Robert A. Binstead、Thomas J. Meyer

  DOI：10.1021/ja000517a

  日期：2001.10.31

  acid and base forms and not from variations in the driving force; (2) competing pathways involving initial electron transfer or initial proton transfer whose relative importance depends on pH; (3) a significant inhibition to outer-sphere electron transfer for the Ru(IV)=O2+/Ru(III)-OH2+ couple because of the large difference in pK(a) values between Ru(IV)=OH3+ (pK(a) < 0) and Ru(III)-OH2+ (pK(a) > 14);

  cis-[Ru(IV)(bpy)2(py)(O)]2+ + H+ + [Os(II)(bpy)3]2+ <==> cis-[ 反应的电子转移动力学Ru(III)(bpy)2(py)(OH)]2+ + [Os(III)(bpy)3]3+ 和顺式-[Ru(III)(bpy)2(py)(OH)]2 + + H++ + [Os(II)(bpy)3]2+ <==> 顺-[Ru(II)(bpy)2(py)(H2O)]2+ + [Os(III)(bpy)3 ]3+ 已通过将 pH 值从 1 改变到 8 在两个方向上进行了研究。动力学是复杂的，但可以通过包括歧化平衡 2cis-[Ru( III)(bpy)2(py)(OH)]2+ <==> (3 x 10(3) M(-1) xs(-1) 向前，2.1 x 10(5) M(-1) xs (-1) 反向) 顺-[Ru(IV)(bpy)2(py)(O)]2+ +
• Macartney, Donal H.; Thompson, David W., Inorganic Chemistry, 1989, vol. 28, # 11, p. 2195 - 2199
  作者：Macartney, Donal H.、Thompson, David W.

  DOI：——

  日期：——
• Macartney, Donal H., Inorganic Chemistry, 1986, vol. 25, # 13, p. 2222 - 2225
  作者：Macartney, Donal H.

  DOI：——

  日期：——