[RuHCl(η2-H2) (P(i-Pr)3)2] | 162338-70-7

• 英文名称: [RuHCl(η2-H2) (P(i-Pr)3)2]
• 英文别名: Ru(H)Cl(H2)(triisopropylphosphine)2；RuHCl(H2)(P(i-Pr)3)2；RuHCl(η2-H2)(P(i)Pr3)2；RuHCl(η2-H2)(PiPr3)2；[RuH(H2)(PiPr3)2]
• CAS: 162338-70-7
• 化学式: C₁₈H₄₅ClP₂Ru
• 分子量: 460.026
• InChiKey: ULGICKJJNZMMCG-UHFFFAOYSA-M

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：

  [RuHCl(η2-H2) (P(i-Pr)3)2] 在 tert-butylethylene 作用下， 以 甲苯 为溶剂， 生成 [RuHCl(PiPr3)2]2
  参考文献：
  名称：

  Coupling of terminal alkynes by RuHXL2 (X=Cl or N(SiMe3)2, L=PiPr3)

  摘要：

  The compounds RuL(2)HX, where L = P(i)Pr(3) and X = Cl or N(SiMe(3))(2), are catalyst precursors for dimerization of terminal alkynes to enynes and also to cumulenes at 23 degrees C; selectivity among these products is X-dependent, but not high. Conversion of Ru species onto the catalytic cycle was undetectably small, so alternative approaches to understanding the catalytic mechanism were employed: stoichiometric reactions, independent synthesis of candidate intermediates, and trapping with CO. These show the intermediacy of vinylidenes and vinyl compounds, and reveal conversion of cumulenes to the thermodynamically more stable enynes. (C) 2007 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2007.12.016
• 作为产物：
  描述：

  Ru(H2)Cl(η2-C6H4CHNCH3)(P(CH(CH3)2)3)2 以 氘代苯 为溶剂， 生成 [RuHCl(η2-H2) (P(i-Pr)3)2] 、 RuCl(η2-C6H4CHNCH3)(P(CH(CH3)2)3)2
  参考文献：
  名称：

  Cleavage of H−C(sp²) and C(sp²)−X Bonds (X = Alkyl, Aryl, OR, NR₂):  Facile Decarbonylation, Isonitrile Abstraction, or Dehydrogenation of Aldehydes, Esters, Amides, Amines, and Imines by [RuHCl(PⁱPr₃)₂]₂

  摘要：

  The RuHClL2 fragment (L = (PPr3)-Pr-i) reacts at 25 degrees C with a dozen different G=CHE compounds (G = O, E = R, OR, NR2; G = NR, E = R) to give ct-acid abstraction products, RuHCl(CG)L-2, and E-H. For E-H = C2H5OH, alcohol is decarbonylated in a second step to give an additional CO ligand and CH4. For E-H = HNR(CR'H-2), amine can be dehydrogenated by RuHClL2 to give RuH(H-2)ClL2 and CR'(2)=NR. X-ray crystallographic studies are presented for the DMF decarbonylation intermediate Ru(H)(2)Cl(eta(2)-C(O)NMe2)L-2, where the strong reducing potential of RuHClL2 is manifested in the formally Ru(IV) species obtained from oxidative addition of H-C(O)NMe2. The structure of Ru(H-2)Cl(eta(2)-C6H4CH=NMe)L-2, the product from aryl C-H activation of benzylidenemethylamine, PhHC=NMe, is also presented. This ability to abstract CO, isonitrile, or H-2 is traced to the considerable pi-basicity of RuHCl((PPr3)-Pr-i)(2).

  DOI：

  10.1021/om000390y

文献信息

• ROMP using heterocyclic carbenes bearing a hydride ligand. An improved synthesis of RuCl2(PR3)2(CHMe)
  作者：Joseph N. Coalter III、Kenneth G. Caulton

  DOI：10.1039/b009931g

  日期：——

  heteroatom-stabilized carbene complexes RuHCl(PR3)2[C(X)C3H6] (R = Pri, Cy; X = O, NH) catalyze the ring-opening metathesis polymerization of 2-norbornene to give mainly (85%) trans-polynorbornene (Mw 1.1–2.0 × 105 g mol−1) in arene solvent at 30–80 °C. Initiation is slow, but not dependent on free phosphine concentration because the catalyst has an empty coordination site cis to the carbene. Protonation of

  环状，杂原子稳定的卡宾络合物RuHCl（PR 3）2 [ C（X）C 3 H 6 ]（R = Pr i，Cy; X = O，NH）催化2-降冰片烯的开环易位聚合在30-80°C的芳烃溶剂中主要生成（85％）反式-聚降冰片烯（M w 1.1–2.0×10 5 g mol -1）。引发缓慢，但不取决于游离膦的浓度，因为催化剂对卡宾具有顺式的顺式配位位点。RuHCl（PR 3）2 [C（OR）R']物种出现在氢化物配体上，所得物种的酸度导致C-OR键断裂。这导致HCl将RuHClL 2 [C（OEt）Me]轻松转化为RuCl 2 L 2 [ CHMe]和EtOH，因此方便简便地合成了卡宾源为H 2 C C（OEt）的传统复分解催化剂）H。
• Geminal dehydrogenation of ether and amine C(sp3)H2 groups by electron-rich Ru(ii) and OsElectronic supplementary information (ESI) available: crystallographic data, fractional coordinates and isotropic thermal parameters, anisotropic thermal parameters, and bond distances and angles. See http://www.rsc.org/suppdata/nj/b2/b200168n/
  作者：German Ferrando-Miguel、Joseph N. Coalter III、Hélène Gérard、John C. Huffman、Odile Eisenstein、Kenneth G. Caulton

  DOI：10.1039/b200168n

  日期：2002.6.7

  Os(H)3Cl[C(NH)(CH2)3](PiPr3)2, together with H2. Os(H)2Cl2(PiPr3)2 is first dehydrochlorinated by one mole of pyrrolidine, then a second mole of pyrrolidine is geminally dehydrogenated to form Os(H)3Cl[C(NH)(CH2)3](PiPr3)2. The five-coordinated carbene OsHCl[CO(CH2)3](PiPr3)2 will add H2, and the resulting product exists as two isomers, a trihydride with Cl cis to the carbene and a species with Cl trans to carbene

  [RuHCl（P i Pr 3）2 ] 2与THF或二氧戊环的反应将碳α双重脱氢成氧，生成RuHCl（H 2）（P i Pr 3）2以及配位环状卡宾RuHCl [ CO （CH 2）2 E]（P i Pr 3）2，其中E = CH 2或O。在存在作为氢受体的CH 2 CH t Bu的情况下，所有Ru都转化为其卡宾络合物。环状胺RN（CH 2）4 （R ＝H，Me）类似地反应，通过双键脱氢产生N-取代的卡宾配合物；给出了R = H的卡宾配合物的晶体结构，揭示了分子间的NH Cl氢键。在H 2 C CH t Bu存在下，在25 °C下对Os（H）3 Cl（P i Pr 3）2建立了相似的化学反应，得到OsHCl [ CO（CH 2）3 ]（P i Pr 3）2。吡咯烷在25 °C下快速反应，首先生成11：1胺加合物，然后缓慢地将三氢化碳卡宾Os（H）3 Cl [ C（NH）（CH 2）3 ]（P
• Monosubstituted Borane Ruthenium Complexes RuH₂(η²:η²-H₂BR)(PR′₃)₂: A General Approach to the Geminal Bis(σ-B–H) Coordination Mode
  作者：Yann Gloaguen、Gaëtan Bénac-Lestrille、Laure Vendier、Ulrike Helmstedt、Eric Clot、Gilles Alcaraz、Sylviane Sabo-Etienne

  DOI：10.1021/om400610k

  日期：2013.9.9

  borane bis(σ-B–H) ruthenium complexes RuH2(η2:η2-H2BR)(PR′3)2 (R = alkyl, aryl; R′ = Cy, Cyp, iPr) has been prepared by using two synthetic strategies. The first one is based on a simple substitution reaction by adding the corresponding monosubstituted H2BR borane to the bis(dihydrogen) ruthenium complex RuH2(η2-H2)2(PCy3)2. The second one, more general, results from the reaction of the chloro complex

  一系列硼烷的双（σ-B-H）的钌络合物期RuH 2（η 2：η 2 -H 2 BR）（PR' 3）2（R =烷基，芳基; R'= CY，的Cyp，我PR）通过使用两种综合策略来准备。第一种是通过将相应的单取代的CH类上的简单取代反应2 BR硼烷的双（二氢酯）钌络合物期RuH 2（η 2 -H 2）2（PCY 3）2。第二个，更一般地，从氯的反应复合物RuHCl（H结果2）（PR' 3）2（R'= Cy，Cyp，i Pr）和相应的单取代的硼氢化锂RBH 3 Li（R = Mes，t Bu，Me，C 4 H 3 S，Ph）。所有配合物均已通过多核NMR，IR和X射线衍射研究进行了表征。DFT计算已被用来更好地定义硼烷配体与金属中心的键合模式，以及建立描绘配位过程的热力学循环。所述吨卜物种显示一个动态行为证明硼氢化物和σ -硼烷制剂之间的平衡。噻吩基情况说明了硫配位与双（σ-B–H）配位模式之间的竞争。
• Geminal dehydrogenation of a C(sp3) CH2 group by unsaturated Ru(II) or Os(II)
  作者：Joseph N. Coalter, III、German Ferrando、Kenneth G. Caulton

  DOI：10.1039/b007200l

  日期：——

  Dimeric [RuHClL2]2 (L = PPr3i), a source of the 14-electron fragment RuHClL2, reacts at reflux in THF to cleanly form equimolar L2HClRuC(CH2)3O and RuHCl(H2)L2, the products of stoichiometric geminal dehydrogenation of the α-C of THF. The same products are produced slowly at 25 °C by reaction of the transient RuHClL2. Double dehydrogenation of the sp3 α-C of THF is also effected at 25 °C by Os(H)3ClL2 if two H ligands are removed with But(H)CCH2.

  二聚体 [RuHClL2]2 (L = Ppr3i)，14 电子片段的来源 RuHClL2，在 THF 中回流反应，干净地形成等摩尔的 L2HClRuC(CH2)3O 和 RuHCl(H2)L2，化学计量的产物 THF α-C 的孪生脱氢。相同 通过瞬态反应在 25°C 下缓慢生成产物 RuHClL2。如果有两个 H 配体，THF 的 sp3 α-C 的双重脱氢也会在 25 °C 下通过 Os(H)3ClL2 进行 用 But(H)C 去除。
• Dimethylaminoborane (H₂BNMe₂) Coordination to Late Transition Metal Centers: Snapshots of the B–H Oxidative Addition Process.
  作者：Gaëtan Bénac-Lestrille、Ulrike Helmstedt、Laure Vendier、Gilles Alcaraz、Eric Clot、Sylviane Sabo-Etienne

  DOI：10.1021/ic201573q

  日期：2011.11.7

  recently reported osmium analogue which was originally formulated as a σ-B–H borinium complex [OsH2Cl(HBNMe2)(PiPr3)2] (4). All our data are in favor of a bis(σ-B–H) coordination mode at a very activated stage in the case of the ruthenium complex 2, whereas in the osmium complex 4, full oxidative addition is favored leading to a complex better formulated as an osmium(IV) boryl species with an α-agostic

  cyclodiborazane的反应〔我2的N- BH 2 ] 2与氯（二氢）钌络合物RuHCl（η 2 -H 2）（P我镨3）2（1）导致了unsymmetricaly协调二甲基氨基络合物RuHCl的形成（H 2 BNMe 2）（P i Pr 3）2（2）。二甲基氨基硼烷（H 2 BNMe 2）与钌中心的配位比例为2通过结合X射线，多核NMR和密度泛函理论（DFT）技术进行了仔细研究，并与最近报道的类似物进行了比较，which类似物最初被制成σ-B-H硼配合物[OsH 2 Cl（HBNMe 2） （P i Pr 3）2 ]（4）。对于钌络合物2，我们的所有数据都支持在非常活化阶段的双（σ-B–H）配位模式，而在complex络合物4的情况下，完全氧化加成有利于形成更好的配合物作为具有α-声B-H相互作用的an（IV）硼基物质。对称二氢配合物RuH的合成与表征为了比较，报道了将二甲基氨基硼氢化锂添加到1中得到的2（H