RuCl(OAc)(PPh3)3 | 55978-89-7

• 物质功能分类: 有机原料 - 羧酸类化合物及衍生物 - 羧酸酯及其衍生物
• 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: RuCl(OAc)(PPh3)3
• 英文别名: chlororuthenium(1+);triphenylphosphane;acetate
• CAS: 55978-89-7
• 化学式: C₅₆H₄₈ClO₂P₃Ru
• 分子量: 982.44
• InChiKey: CBECNVOKQNQZIN-UHFFFAOYSA-L

物化性质

• 熔点：
  223-244°C

计算性质

• 辛醇/水分配系数(LogP)：
  9.78
• 重原子数：
  63
• 可旋转键数：
  9
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.02
• 拓扑面积：
  40.1
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• WGK Germany：
  3

反应信息

• 作为反应物：
  描述：

  双(2-二苯基膦乙基)苯基磷 、 RuCl(OAc)(PPh3)3 以 甲苯 为溶剂， 反应 2.5h， 以84%的产率得到
  参考文献：
  名称：

  含三膦的钌-乙酰基络合物：合成、表征、DFT、mer/fac 异构化和甲酸脱氢

  摘要：

  摘要 本课题组合成的含三膦的钌-乙酰基络合物[RuCl(κ2-OAc)(triphos)] (2)和新的类似物[RuCl(κ2-OAc)(etp)] (1) (triphos = 1 ,1,1-三(二苯基膦基甲基)乙烷或etp = 双[2-(二苯基膦基)乙基]苯基膦)被评估为甲酸(FA)脱氢的预催化剂。复合物 [RuCl(κ2-OAc)(etp)] (1) 通过 1H、13C 和 31P{1H} NMR、振动光谱、元素分析和 X 射线衍射进行了充分表征。通过循环伏安法检查1和2的电化学行为。进行并讨论了 1、2 和 1 的两种异构体（1' 和 1”）的 DFT 计算。由于 etp 配体的线性性质，[RuCl(κ2-OAc)(etp)] (1' 和 1") 的三种异构形式是可能的并且被观察到。在 80 °C 的三种溶剂（MeOH、THF 和 iPrOH）中，这两种配合物对 FA 的分解都很活跃，仅导致

  DOI：

  10.1016/j.molstruc.2019.127129
• 作为产物：
  描述：

  diruthenium(II,III) tetraacetatechloride 在 三苯基膦 作用下， 以 甲醇 为溶剂， 以60%的产率得到RuCl(OAc)(PPh3)3
  参考文献：
  名称：

  均相钌络合物催化剂液相脱氢甲醇

  摘要：

  甲醇的催化脱氢以均相钌（II）配合物进行，在溶液的回流条件下产生甲醛和二氢作为主要产物。研究了添加剂对氯化锂、乙酸锂、乙酸和乙基二苯基膦的初始反应速率的影响。通过在反应过程中用 H 和 CO 配体置换双齿 OAc 配体，催化剂络合物 [Ru(OAc)Cl(PEtPh2)3] 逐渐失活。这些顺式布置的位点将用于分裂 C-H 键。提出了催化反应循环，其中包括催化剂配合物的溶剂分解、OCH3 配体的 β-H 消除和乙酸对氢化物中间体的攻击以产生二氢等过程。

  DOI：

  10.1246/bcsj.61.2291

文献信息

• Dehydrogenation of methanol in the liquid phase with a homogeneous ruthenium complex catalyst
  作者：Sumio Shinoda、Hiroaki Itagaki、Yasukazu Saito

  DOI：10.1039/c39850000860

  日期：——

  Catalytic dehydrogenation of methanol occurs in solution by use of a homogeneous ruthenium complex,[Ru2(OAc)4Cl]–t-phosphine, or mononuclear ruthenium(II) complexes, which can be isolated from the reaction solution as catalysts.

  甲醇的催化脱氢是通过使用均相的钌络合物[Ru 2（OAc）4 Cl] -t-膦或单核钌（II）络合物进行的，可以将其作为催化剂从反应溶液中分离出来。
• Synthesis and Structures of NCN Pincer-Type Ruthenium and Iridium Complexes Bearing Protic Pyrazole Arms
  作者：Tatsuro Toda、Koki Saitoh、Akihiro Yoshinari、Takao Ikariya、Shigeki Kuwata

  DOI：10.1021/acs.organomet.7b00065

  日期：2017.3.27

  The reaction of the 1,3-bis(pyrazol-3-y1)benzenes 1 with [RuC1(OAc)(PPh3)3] resulted in selective C-H cleavage at the 2-position of 1 to give the protic NCN pincer-type ruthenium(II) complexes [RuCl(R-NCN-LH2)-(PPh3)2] (2; R-NCN-LH2 = 4-R-2,6-bis(5-tert-buty1-1H-pyrazol-3-yl)pheny1). Similar cyclometalation with iridium tri-chloride followed by addition of triphenylphosphine led to the formation of the iridium(III) analogue [IrCI(Bu-t-NCN-LH2)(PPh3)]Cl (5). Treatment of the ruthenium complexes 2 with carbon monoxide afforded the carbonyl complexes [Ru( CO) (R-NCN-LH2) (PPh3)2] CI (4). On the other hand, the pyridine analogue of 1, 2,6-bis(5-tert-butyl-1H-pyrazol-3-yl)pyridine (NNN-LH2), reacted with iridium trichloride to yield the protic NNN pincer-type complex [IrC1(3)(NNN-LH3)] (7). The stronger r donation of the NCN pincer-type ligand in comparison with the analogous NNN ligand was suggested by the CO stretching frequencies of the ruthenium carbonyl complexes 4 as well as the M-Cl distances. The catalytic activity of the ruthenium complexes 2a,b toward transfer hydrogenation of a ketone was also evaluated.
• Preparation of RuCH2PMe2(PMe3)3Cl, Ru(CH2PMe2)2(PMe3)2, and Rh2(CH2PMe2)2(PMe3)4 and their reactions with hydrogen
  作者：Vera V. Mainz、Richard A. Andersen

  DOI：10.1021/om00083a005

  日期：1984.5
• Reactivity and Catalytic Activity of a Robust Ruthenium(II)−Triphos Complex
  作者：Adrian B. Chaplin、Paul J. Dyson

  DOI：10.1021/ic701773a

  日期：2008.1.1

  The ruthenium(II)-triphos acetatc, complex [RuCl(OAc)(k(3)-triphos)] (triphos = (PPh2CH2)(3)CMe) has been found to be an active catalyst precursor for the hydrogenation of 1-alkenes under relatively mild conditions (5-50 bar H-2, 50 degrees C). In contrast to related triphenylphosphine complexes, [RuCl(OAc)(k(3)-triphos)] is much less air sensitive and 14 high catalytic activities were achieved when catalyst samples were prepared without exclusion of air or moisture. Substitution of the acetatc, ligand can be effected by treatment of acid, affording [Ru-2(mu-Cl)(3)(k(3)-triphos)(2)]Cl and [RuCl(k(3)-triphos)](2)(BF4)(2) with aqueous HCl and [Et2OH]BF4, respectively, or by heating with dmpm in the presence of [NH4]PF6, resulting in formation of [RuCl(k(2)-dMPM)(k(3)-triphos)]PF6 (dmpm = PMe(2)CH(2)PMe2). A hydride complex, [RuHCl (k(3)-triphos)], formed by acetato-mediated heterolytic cleavage of dihydrogen is proposed as the active catalytic species. An inner-sphere, monohydride mechanism is suggested for the catalytic cycle, with chloro and triphos ligands playing a spectator role. These mechanistic proposals are consistent with reactivity studies carried out on [RuCl(OAc) (k(3)-triphos)] and [RuH(OAc)(k(3)-triphos)] and supported by a computational analysis. The solid-state structures of [RuCl(OAc)(k(3)-triphos)], [RuCl(k(3)-triphos)](2)(BF4)(2), and [RUCl(k(2)-dmpm)(k(3)-triphos)]PF6 have been established by X-ray diffraction.