mer-tris(2-diphenylphosphinobenzenethiolate)ruthenium(III) | 143499-56-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: mer-tris(2-diphenylphosphinobenzenethiolate)ruthenium(III)
• 英文别名: [tris(2-(diphenylphosphino)thiaphenolato)ruthenium(III)]；(2-diphenylphosphinothiaphenolate)3-ruthenium(III)；[Ru-1]；tris(2-diphenylphosphinobenzenethiolato)ruthenium(III)；[tris(2-diphenylphosphinebenzenethiolato)ruthenate(III)]；[Ru(DPPBT)]
• CAS: 143499-56-3
• 化学式: C₅₄H₄₂P₃RuS₃
• 分子量: 981.117
• InChiKey: PAUJJEOQOYUHAS-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  10.05
• 重原子数：
  61.0
• 可旋转键数：
  6.0
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  mer-tris(2-diphenylphosphinobenzenethiolate)ruthenium(III) 以 丙酮 为溶剂， 生成 (2-diphenylphosphinothiaphenolate)3-(ruthenium(IV))(1+)
  参考文献：
  名称：

  在钌配位的噻吩基和甲基酮之间形成碳-硫键。

  摘要：

  DOI：

  10.1002/anie.200462713
• 作为产物：
  描述：

  [bis(triphenylphosphoranylidene)ammonium][Ru(diphenylphosphinobenzenethiolate)3] 在 碘 作用下， 以 甲醇 为溶剂， 以72%的产率得到mer-tris(2-diphenylphosphinobenzenethiolate)ruthenium(III)
  参考文献：
  名称：

  Electrochemical Investigations of the [Tris(2-(diphenylphosphino)thiaphenolato)ruthenate(II)] Monoanion Reveal Metal- and Ligand-Centered Events: Radical, Reactivity, and Rate

  摘要：

  Electrochemical investigations of [bis(triphenylphosphoranylidene)ammonium)][tris(2-(diphenylphosphino)thiaphenolato)ruthenate(II)], PPN[Ru(DPPBT)(3)] (1), and [(bis(2-(diphenylphosphino)thiaphenolato)methane)(2-(diphenylphosphino)thiaphenolato)ruthenium(II)] chloride, [Ru((DPPBT)(2)CH2)(DPPBT)]Cl (2) are reported. Complex 1 is oxidized reversibly in a metal-centered event by one electron at a potential of +455 mV (vs Ag/AgCl) to the ruthenium(III) derivative [tris(2-(diphenylphosphino)thiaphenolato)ruthenium(III)], 3. Complex 3 can also be prepared by iodine oxidation of 1 in acetonitrile. Oxidation of 3 in acetonitrile is reversible on a cyclic voltammetry time scale but irreversible upon bulk oxidation yielding Ru-X. Monitoring the oxidation of 3 by UV-visible spectroscopy reveals a proposed metal-coordinated thiyl radical intermediate with a maximum absorbance at 850 nm. This intermediate decays at a temperature of -20degreesC with a rate constant of (5.82 +/- 0.73) x 10(-3) s(-1) with a small, positive DeltaH(double dagger) and a large, negative DeltaS(double dagger). Ru-X can be oxidized reversibly to Ru-Y at a potential of +806 mV but cannot be reduced. Complex 2 is reversibly oxidized by one electron in a metal-centered event to 4 at a potential of +767 mV.

  DOI：

  10.1021/ic035085u

文献信息

• Carbon−Sulfur Bond Formation via Alkene Addition to an Oxidized Ruthenium Thiolate
  作者：Craig A. Grapperhaus、Kiran B. Venna、Mark S. Mashuta

  DOI：10.1021/ic701078e

  日期：2007.9.1

  (DPPBT = 2-diphenylphosphinobenzenethiolate) in the presence of ethylene yields [(ethane-1,2-diylbis(thio-2,1-phenylene)diphenylphosphine) ruthenium(II)] hexafluorophosphate, [2a]PF6, from the addition of the alkene across cis sulfur sites. During oxidation, the absorption bands of 1b at 540, 797, and 1041 nm decrease in intensity. The resulting complex [2a]+ displays a single redox couple at +804 mV.

  在乙烯存在下[Ru（DPPBT）3]，1b，（DPPBT = 2-二苯基膦基苯硫醚）的本体氧化生成[（乙烷-1,2-二基双（硫代-2,1-亚苯基）二苯基膦）钌（II）六氟磷酸盐，[2a] PF6，来自顺式硫位点上的烯烃加成。在氧化过程中，1b在540、797和1041 nm处的吸收带强度降低。所得的复合物[2a] +在+804 mV处显示单个氧化还原对。[2a] +的+ ESI-MS在m / z = 1009.1013处显示一个母离子峰，并且31P NMR谱图显示的delta（1）= 61.0，delta（2）= 40.3和delta（3 ）= 37.5，耦合常数J（12）约为J（13）约30 Hz，J（23）= 304 Hz。在+1000 mV的保持电势下，一个电子氧化[2a] +会产生[（乙烷-1,2-二基双（硫代-2，1-亚苯基）二苯基膦）钌（III）六氟磷酸盐，[2b] [PF6]
• Singlet Diradical Character of an Oxidized Ruthenium Trithiolate: Electronic Structure and Reactivity
  作者：Craig A. Grapperhaus、Pawel M. Kozlowski、Devesh Kumar、Holly N. Frye、Kiran B. Venna、Selma Poturovic

  DOI：10.1002/anie.200700297

  日期：2007.5.25