[bis(triphenylphosphoranylidene)ammonium][Ru(diphenylphosphinobenzenethiolate)3] | 462094-51-5

• 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: [bis(triphenylphosphoranylidene)ammonium][Ru(diphenylphosphinobenzenethiolate)3]
• 英文别名: [PPN][Ru(2-diphenylphosphinobenzenethiolato)3]；[PPN][Ru(2-diphenylphosphinobenzene thiolate)3]；[bis(triphenylphosphoranylidene)ammonium][Ru(2-diphenylphosphinobenzenethiolato)3]；2-diphenylphosphanylbenzenethiolate;ruthenium(2+);triphenyl-[(triphenyl-λ5-phosphanylidene)amino]phosphanium
• CAS: 462094-51-5
• 化学式: C₃₆H₃₀NP₂*C₅₄H₄₂P₃RuS₃
• 分子量: 1519.71
• InChiKey: IPYBSKJGBNSENZ-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  17.12
• 重原子数：
  100
• 可旋转键数：
  13
• 环数：
  15.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  15.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  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]
• Dichloromethane Alkylates a Trithiolato-Ruthenium Complex to Yield a Methylene-Bridged Thioether Core. Synthesis and Structural Comparison to the Thiolato-Ruthenium Precursor
  作者：Craig A. Grapperhaus、Selma Poturovic、Mark S. Mashuta

  DOI：10.1021/ic025735e

  日期：2002.8.1

  ammonium), 1, from chlorobenzene/ether as light-orange crystalline plates, and the X-ray crystal structure has been determined. In dichloromethane, the cis positioned thiolates are alkylated by solvent yielding the methylene-bridged triphosphino/dithioether/thiolato complex [(bis-(2-diphenylphosphinothiaphenolato)methane)(2-diphenyl-phosphinothiaphenolato)ruthenium(II)]chloride, [Ru((DPPBT)(2)CH(2))(DPPBT)]Cl

  先前报道的三膦/三硫代镧钌阴离子[tris-（2-diphenylphosphinothia-phenolato）ruthenium（II）]（-），[Ru（DPPBT）（3）]（-）已作为PPN盐（ PPN =双（三苯基三氟膦基亚铵）铵，来自氯苯/醚，为浅橙色结晶板，并且已确定X射线晶体结构。在二氯甲烷中，顺式硫醇盐通过溶剂进行烷基化，生成亚甲基桥连的三膦基/二硫醚/硫醇基络合物[（（双-（2-二苯基膦硫酚基）甲烷）（2-二苯基膦硫酚基）钌（II）]氯化物，[Ru（ （DPPBT）（2）CH（2））（DPPBT）] Cl（2）。1的己烷溶液分层的二氯甲烷溶液生成2，为橙色立方体。烷基化硫醚产物中钌-硫键的距离比硫醇盐前体中的短。在2之内
• Oxygenation of a Ruthenium(II) Thiolate to a Ruthenium(II) Sulfinate Proceeds via Ruthenium(III)
  作者：Craig A. Grapperhaus、Selma Poturovic、Mark S. Mashuta

  DOI：10.1021/ic051211d

  日期：2005.11.1

  ylidene); DPPBT = 2-diphenylphosphinobenzene thiolate] to oxygen initiates metal-centered oxidation, yielding the ruthenium(III) thiolate Ru(DPPBT)3. Ru(DPPBT)3 further reacts with oxygen, at sulfur, to give the ruthenium(III) sulfinate complex [Ru(DPPBT-O2)2(DPPBT)], which is reduced under ambient conditions to [PPN][Ru(DPPBT-O2)2(DPPBT)]. Ruthenium(II) sulfinate is the only product isolated from

  [PPN] [Ru（DPPBT）3]的乙腈/甲醇溶液的暴露 DPPBT = 2-二苯基膦基硫醇盐]引发氧为中心的金属氧化反应，生成硫醇钌（III）Ru（DPPBT）3。Ru（DPPBT）3与硫进一步在氧气中反应，生成亚硫酸钌（III）络合物[Ru（DPPBT-O2）2（DPPBT）]，在环境条件下将其还原为[PPN] [Ru（DPPBT- O2）2（DPPBT）]。亚硫酸钌（II）是从乙腈/甲醇中分离出的唯一产物。获得[PPN] [Ru（DPPBT-O2）2（DPPBT）]的黄色晶体。在氯苯/己烷中氧化[PPN] [Ru（DPPBT）3]时，分离出亚硫酸钌（III），为绿色棱柱形晶体。亚硫酸钌（II）的电化学氧化产生了钌（III）衍生物，