dihydridotris(triphenylphosphine)ruthenium | 913564-49-5

• 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: dihydridotris(triphenylphosphine)ruthenium
• 英文别名: Ru(H)2(PPh3)3；RuH₂(CO)(PPh₃)₃；RuH₂(PPh₃)₃；[H2Ru(PPh3)3]；RuH2(PPh3)3；ruthenium dihydride;triphenylphosphane
• CAS: 913564-49-5；30352-62-6
• 化学式: C₅₄H₄₇P₃Ru
• 分子量: 889.958
• InChiKey: SCMCPXZQXJENKP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.8
• 重原子数：
  58.0
• 可旋转键数：
  12.0
• 环数：
  9.0
• 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：
  0.0

反应信息

• 作为反应物：
  描述：

  dihydridotris(triphenylphosphine)ruthenium 、 三苯甲基亚硝基硫醚 以 乙醇 、 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Trityl thionitrite: a potential transfer nitrosating agent for metal nitrosylation

  摘要：

  DOI：

  10.1016/s0020-1693(00)80567-8
• 作为产物：
  描述：

  Ru(PPh3)₃HCl*toluene 在 potassium hydride 作用下， 以 氘代甲苯 为溶剂， 生成 dihydridotris(triphenylphosphine)ruthenium
  参考文献：
  名称：

  Roles of neutral and anionic ruthenium polyhydrides in the catalytic hydrogenation of ketones and arenes

  摘要：

  DOI：

  10.1021/ja00244a019
• 作为试剂：
  描述：

  4-N-benzyl-2-N,2-N,6-trimethyl-1,3,5-triazine-2,4-diamine 、 苯甲醇 在 tris(triphenylphosphine)ruthenium(II) chloride 、 dihydridotris(triphenylphosphine)ruthenium 、 potassium tert-butylate 作用下， 以 1,4-二氧六环 为溶剂， 反应 16.0h， 生成 N²-benzyl-N⁴,N⁴-dimethyl-6-phenethyl-1,3,5-triazine-2,4-diamine
  参考文献：
  名称：

  钌催化1,3,5-三嗪甲基与醇的发散烷基化和烯烃化

  摘要：

  通过选择钌催化剂，已开发出可控制的烷基1,3,5-三嗪甲基与醇的烷基化或烯烃化反应。这种方法在克级反应中的成功应用表明它具有大量合成的潜力。

  DOI：

  10.1002/ejoc.202000781

文献信息

• Efficient and Selective Aerobic Oxidation of Alcohols into Aldehydes and Ketones Using Ruthenium/TEMPO as the Catalytic System
  作者：Arné Dijksman、Arturo Marino-González、Antoni Mairata i Payeras、Isabel W. C. E. Arends、Roger A. Sheldon

  DOI：10.1021/ja0103804

  日期：2001.7.1

  The combination of RuCl2(PPh3)3 and TEMPO affords an efficient catalytic system for the aerobic oxidation of a variety of primary and secondary alcohols, giving the corresponding aldehydes and ketones, in >99% selectivity in all cases. The Ru/TEMPO system displayed a preference for primary vs secondary alcohols. Results from Hammett correlation studies (rho = -0.58) and the primary kinetic isotope

  RuCl2(PPh3)3 和 TEMPO 的组合为各种伯醇和仲醇的有氧氧化提供了一个有效的催化系统，产生相应的醛和酮，在所有情况下的选择性都超过 99%。Ru/TEMPO 系统显示出对伯醇和仲醇的偏好。Hammett 相关性研究 (rho = -0.58) 和催化需氧苯甲醇氧化的主要动力学同位素效应 (kH/kD = 5.1) 的结果与氧钌 (O=Ru) 或基于氧铵的机制不一致。我们假设了一种氢化金属机制，涉及“RuH2(PPh3)3”物种作为活性催化剂。TEMPO 作为氢转移介质，在催化有氧条件下通过氧气再生，或在化学计量厌氧条件下转化为 TEMPH。
• [EN] NOVEL TRANSITION METAL COMPLEXES, THEIR PREPARATION AND USE<br/>[FR] NOUVEAUX COMPLEXES DE MÉTAUX DE TRANSITION, LEUR PRÉPARATION ET UTILISATION
  申请人：LANXESS DEUTSCHLAND GMBH

  公开号：WO2014187973A1

  公开（公告）日：2014-11-27

  Novel transition metal complexes are provided which represent viable catalysts for a broad variety of reactions such as hydrogenation reactions and metathesis reactions. Novel preparation processes are made available via unprecedented routes inter alia not involving structures according to Grubbs I or Grubbs II catalysts.

  提供了新型过渡金属配合物，这些配合物可作为广泛反应的催化剂，如加氢反应和醇醚交换反应。通过前所未有的途径提供了新颖的制备方法，其中不涉及Grubbs I或Grubbs II催化剂的结构。
• Catalytic activity of dihydride ruthenium complexes in the hydrogenation of nitrogen containing heterocycles
  作者：Piero Frediani、Valentina Pistolesi、Marco Frediani、Luca Rosi

  DOI：10.1016/j.ica.2005.06.025

  日期：2006.2

  selectivity of these catalytic systems in the hydrogenation of quinoline: in all tests the three catalysts lead to 1,2,3,4-tetrahydroquinoline as the major product, furthermore this compound is the only formed in the presence of RuH2(CO)2(PPh3)2. The selectivity is affected by the presence of an acid (CH3COOH) or a base (NnBu3) in the reaction media. The complex RuH2(PPh3)4 is catalytically active, even if

  摘要分析了二水合钌配合物RuH2（CO）2（PnBu3）2，RuH2（CO）2（PPh3）2和RuH2（PPh3）4在含氮杂环加氢中的催化活性。反应参数（例如温度，氢气压力，催化剂浓度）对反应速率和区域选择性的影响。RuH2（PPh3）4表现出更好的催化活性，在100°C和25 bar氢气压力下24小时后，喹啉的转化率为86.7％，而RuH2（CO）2（PPh3）2和RuH2（CO）2（PnBu3） ）2在相同条件下的转化率分别为37.1％和35.6％。这些结果由喹啉的氢化反应速率证实，因为在RuH2（PPh3）4存在下的Kc（1.46×10-5 s-1）高于其他（6.37×10-6 s-1） RuH2（CO）2（PPh3）2和6。对于RuH2（CO）2（PnBu3）2）为36×10-6 s-1。值得注意的是这些催化剂体系在喹啉加氢中的选择性：在所有测试中，三种催化剂均以1,2,3,4-四
• Coordination chemistry of NSO−, NSO2− and S3N− ligands: comparison of electronic structure of RhNSO, RhSH and RhCl complexes
  作者：Krishna K. Pandey

  DOI：10.1016/s0020-1693(00)90151-8

  日期：1991.4

  CsNSO2 reacts with fluoro complexes, trans-[M(CO)F(PPh3)2] (M = Rh, Ir) to give sulfonylnitrido complexes, trans-[M(CO)(NSO2)(PPh3)2] which react with triphenylphosphine to afford thionitro complexes, trans-[M(CO)(NSO)(PPh3)2]. The thionitro complexes are also prepared by the reaction of CsNSO2 with hydrido complexes, [MH(CO)(PPh3)3]. Reaction of CsNSO2 with [RuH2(CO)(PPh3)2] yields [Ru(CO)(NSO2)2(PPh3)2]. The sulfonylnitrido complexes of the type Cs2[M'(NS)(NSO2)2Cl3] (M' = Ru, Os) are prepared by the reaction of CsNSO2 and [M'(NS)Cl3]. The reactions of heptasulfurimide with [RhCl(PPh3)3] and [Rh(CO)Cl(PPh3)2] afford disulfidothinitrato complexes [Rh(S3N)(PPh3)2] and [Rh(CO)(S3N)(PPh3)2], respectively. CNDO/2 molecular orbital calculations have been performed on the model systems trans-[Rh(CO)L(PH3)2] (L = NSO, SH, Cl) in order to investigate the nature and energetics of the interaction between rhodium and NSO, SH, Cl ligands. The computed trends for Rh-X, Rh-C and C-O bond strengths, as measured by Wiberg indices and charge distributions, suggest that the strength of the coordination bond Rh-L increases in the order [Rh-NSO] < [Rh-Cl] < [Rh-SH] and the strength of the Rh-C bond increases in the order [Rh(CO)Cl(PH3)2] < [Rh(CO)(NSO)-(PH3)2] < [Rh(CO)(SH)(PH3)2]. The trend in C-O bond strength is [Rh(CO)Cl(PH3)2] > [Rh(CO)(NSO)-(PH3)2] > [Rh(CO)(SH)(PH3)2]. The NSO group is the worst pi-acceptor amongst the three ligands.
• Pandey, K. K.; Paleria, V.; Nehete, D. T., Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 1990, vol. 20, p. 1169 - 1184
  作者：Pandey, K. K.、Paleria, V.、Nehete, D. T.

  DOI：——

  日期：——