{Ru(CO)ClH(3,5-dimethylpyrazole)(PPh3)2} | 106583-99-7

• 英文名称: {Ru(CO)ClH(3,5-dimethylpyrazole)(PPh3)2}
• CAS: 106583-99-7
• 化学式: C₄₂H₃₉ClN₂OP₂Ru
• 分子量: 786.255
• InChiKey: PXBWFVSMTSIJQV-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：

  {Ru(CO)ClH(3,5-dimethylpyrazole)(PPh3)2} 以 乙醇 、 二氯甲烷 为溶剂， 生成 {Ru(CO)Cl(CCC3H7)(3,5-dimethylpyrazole)(PPh3)2}
  参考文献：
  名称：

  [Ru（CO）ClH（Me2Hpz）（PR3）2]（Me2Hpz = 3,5-二甲基吡唑; R = Ph，对甲苯基）与乙炔的反应。[Ru（CO）Cl（HC：CHCMe3）（Me2HPz）（PPh3）2]和[Ru（CO）（MeO2CC：CHCO2Me）（HCO3）（PPh3）2]的晶体结构

  摘要：

  DOI：

  10.1021/om00099a014
• 作为产物：
  描述：

  (Ph3P)2(3,5-dimethylpyrazole)(CO)ClRuCHCHPh 在 乙醇 作用下， 以 乙醇 为溶剂， 以78%的产率得到{Ru(CO)ClH(3,5-dimethylpyrazole)(PPh3)2}
  参考文献：
  名称：

  Phenylacetylene dimerization promoted by ruthenium(II) complexes

  摘要：

  The complex Ru(CO)(CH = CHPh)Cl(C5,H5N)(PPh3)2 and related alkenyl complexes react in methanol or ethanol to give (E,E)-1,4-diphenylbuta-1,3-diene and the ruthenium(II) hydride Ru(CO)H(Cl)(C5H5N)(PPh3)3. Further reaction of this hydride with the butadiene results in 1,2-reduction to yield (E)-1,4-diphenyl-1-butene. However, the reaction of phenylacetylene with catalytic amounts of ruthenium hydrides gave the dimer (Z)-1,4-diphenylbuten-3-yne. On the other hand, the reaction of 1,2-diphenylethenylruthenium(II) derivatives in methanol or ethanol gave trans-stilbene rather than the butadiene. Several deuteriation experiments were performed in order to elucidate the mechanism of formation of (E, E)-1,4-diphenylbuta-1,3-diene and ruthenium hydride from the corresponding alkenyl complexes.

  DOI：

  10.1016/0022-328x(91)86337-p

文献信息

• Pyrazole cleavage of tris(3,5-dimethylpyrazolyl)borate with Ruthenium(II) complexes: Synthesis, structural characterization and DFT studies
  作者：Donkupar Kharbani、Debojit Kumar Deb、Ibaniewkor L. Mawnai、Sunshine D. Kurbah、Biplab Sarkar、E.K. Rymmai

  DOI：10.1016/j.molstruc.2016.11.097

  日期：2017.4

  Abstract The reaction of [Ru(H)(Cl)(CO)(PPh3)3] (1) with KTp* (KTp* = Potassium tris(3,5-dimethylpyrazolyl)borate) in a refluxing toluene yields a mixture of [RuTp*(H)(CO)(PPh3)] (2), [Ru(H)(Cl)(pz*H)(CO)(PPh3)2] (3), and [H(pz*)B(μ-pz*)2B(pz*)H] (4) (pz*H = 3,5-dimethylpyrazole). The products (3) and (4) were obtained by the degradation of the scorpionate ligand, Tp*. These complexes were characterised by

  摘要 [Ru(H)(Cl)(CO)(PPh3)3] (1) 与 KTp*（KTp* = 三（3,5-二甲基吡唑基）硼酸钾）在回流甲苯中反应生成 [ RuTp*(H)(CO)(PPh3)] (2)、[Ru(H)(Cl)(pz*H)(CO)(PPh3)2] (3) 和 [H(pz*)B( μ-pz*)2B(pz*)H] (4) (pz*H = 3,5-二甲基吡唑)。产物 (3) 和 (4) 是通过降解蝎形配体 Tp* 获得的。这些配合物通过 IR、1H NMR、UV、X 射线晶体学和 DFT 计算表征。
• Reactivity of ruthenium(II) complexes with 1-hydroxymethyl- or 1-benzyl-3,5-dimethylpyrazole and similar functionalized bipyrazoles. X-Ray crystal structure of carbonylchlorohydrido(3,5-dimethylpyrazole-N 2)-bis(triphenylphosphine)ruthenium(II)
  作者：Antonio Romero、Angel Vegas、Amelia Santos、Ana M. Cuadro

  DOI：10.1039/dt9870000183

  日期：——

  give binuclear bipyrazole-bridged complexes [Ru(CO)ClH(PPh3)2}2(µ-L′)][L′= 3,3′,5,5′-tetramethyl-4,4′-bipyrazole or -methylenedipyrazole respectively]. No reaction occurs with 1 -benzyl-3,5-dimethylpyrazole nor with the corresponding 1,l′-dibenzylbipyrazole. We have determined the crystal structure of [Ru(CO)ClH(Hdmpz)(PPh3)2](Hdmpz = 3,5-dimethylpyrazole). It crystallizes in the space group P21n with

  络合物[RuCl 2（PPh 3）3 ]，[RuClH（PPh 3）3 ]和[Ru（CO）ClH（PPh 3）3 ]与1-羟甲基-3,5-二甲基吡唑反应，在所有情况下均得到羰基氯氢（3,5-二甲基吡唑-N 2）双（三苯基膦）钌（II）（1a）为产物。这些反应的特征是吡唑环中的氢取代1-羟甲基。用1,1'-二（羟甲基）-3,3'，5,5'-四甲基-4,4'-联吡唑和-亚甲基二吡唑进行类似的反应，得到双核联吡唑桥联的复合物[Ru（CO）ClH （PPh 3）2 } 2（μ-L'）] [L'分别为3,3'，5,5'-四甲基-4,4'-联吡唑或-亚甲基二吡唑]。与1-苄基-3，5-二甲基吡唑或与相应的1，1′-二苄基联吡唑不发生反应。我们确定了[Ru（CO）ClH（Hdmpz）（PPh 3） 2 ]（Hdmpz = 3,5-二甲基吡唑）的晶体结构。它在空间组P 2 1 n中结晶，其中a = 9.687（3），
• The Effect of N-Donor Ligands on the Reaction of Ruthenium Hydrides with 1-Alkynes
  作者：Amelia Santos、Javier López、Amalia Galán、Juan J. González、Pilar Tinoco、Antonio M. Echavarren

  DOI：10.1021/om970054q

  日期：1997.7.1

  Neutral ruthenium hydrides Ru(CO)ClH(L)(PPh3)(2) bearing one N-donor ligand react with 1-alkynes at 23 degrees C to yield neutral alkenyl complexes Ru(CO)Cl(CH=CHR)(L)(PPh3)(2). Under similar conditions, cationic hydride complexes [Ru(CO)H(L)(2)(PPh3)(2)]PF6 with pyridine-type N-donor ligands yield alkynyl complexes [Ru(CO)(CH=CHR)(L)(2)(PPh3)(2)]PF6 as a result of the reaction of the intermediate labile alkenyl with a second molecule of alkyne, Under more forcing conditions, 1-alkynyl complexes could also be prepared from the neutral ruthenium hydrides. Cationic ruthenium hydrides with bidentate N-donor ligands are unreactive toward 1-alkynes, Neutral alkenyl complexes Ru(CO)Cl(CH=CHR)(L)(PPh3)(2) (R = p-MeC6H4, CMe3; L = pyridine, isoquinoline) reacted smoothly with 1-alkynes to afford the corresponding sigma-alkynyl ruthenium derivatives Ru(CO)Cl(C=CR)(L)(PPh3)(2).
• Synthesis of RuHCl(CO)(Hdmpz)(L)2 (L=PPh3, AsPh3, and Hdmpz=3,5-dimethylpyrazole) and crystal structure of RuHCl(CO)(Hdmpz)(AsPh3)2
  作者：Seong Huh、Youngmee Kim、Kyoung-Tae Youm、Moo-Jin Jun

  DOI：10.1016/s0277-5387(99)00179-5

  日期：1999.8

  Treatment of RuHCl(CO)(L)(3) with a slight excess amount of K[HB(3,5-Me(2)pz)(3)] in boiling MeOH solution yielded unusual 3,5-dimethylpyrzaole (Hdmpz) complexes, RuHCl(CO)(Hdmpz)(L)(2) (L=PPh3, 1 or AsPh3, 2). Unexpectedly the dissociation of the bonds between the boron atom and the nitrogen atoms of the potentially tridentate [HB(3,5-Me(2)pz)(3)](-) ligand during the coordination of the ligand to the Ru-II metal has been observed. In a separate preparation, the RuHCl(CO)(Hdmpz)(PPh3)(2) complex has also been synthesized from the reaction between RuHCl(CO)(PPh3)(3) and the monodentate Hdmpz ligand. Complexes 1 and 2 have been characterized by elemental analysis, IR and H-1 NMR spectroscopies. Compound 1 has also been prepared by the reaction between RuHCl(CO)(PPh3)(3) and K[H2B(3,5-Me(2)pz)(2)] in boiling toluene solution. The crystal structure of 2 has been studied by X-ray crystallography. The geometrical structure around Ru-II of 2 is a distorted octahedral structure. The crystal structure of 2 consists of a discrete monomeric compound. It is interesting to find that the sterically-demanding [HB(3,5-Me(2)pz)(3)](-) or [H2B(3,5-Me(2)pz)(2)](-) ligands break up during the reaction with the Ru-II complexes to form the neutral 3,5-dimethylpyrazole complexes. In contrast to these observations, [H(2)Bpz(2)](-) and [H2B(4-Brpz)(2)](-) ligands form very stable Ru-II complexes. (C) 1999 Elsevier Science Ltd. All rights reserved.