[dichloro(p-cymene)(triphenylphosphane)ruthenium(II)] | 52490-94-5

• 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: [dichloro(p-cymene)(triphenylphosphane)ruthenium(II)]
• 英文别名: RuCl2(p-cymene)(PPh3)；Ru(p-cymene)Cl2PPh3；RuCl2(PPh3)(p-cymene)；(p-cymene)RuCl2(PPh3)；RuCl2(PPh3)(η6-p-cymene)；{RuCl2(η6-p-cymene)(PPh3)}；dichlororuthenium;1-methyl-4-propan-2-ylbenzene;triphenylphosphane
• CAS: 52490-94-5
• 化学式: C₂₈H₂₉Cl₂PRu
• 分子量: 568.488
• InChiKey: FDSKFSUVVCGWCM-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.94
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 危险性防范说明：
  P501,P261,P270,P271,P264,P280,P362+P364,P301+P312+P330,P302+P352+P312,P304+P340+P312
• 危险性描述：
  H302+H312+H332
• 储存条件：
  2-8℃

反应信息

• 作为反应物：
  描述：

  [dichloro(p-cymene)(triphenylphosphane)ruthenium(II)] 在 air 作用下， 以 氯仿 为溶剂， 生成 [(η⁶-p-cymene)Ru(μ-Cl)₃RuCl₂(κP-PPh₃)]
  参考文献：
  名称：

  通过在三苯基膦/苯氧基二苯基膦配体上的单取代来 调节钌（ii）对-肉桂烯配合物的细胞毒性†

  摘要：

  新的配合物将[RuCl 2（η 6 - p -cymene）（κ P -Ph 2 PR）] [R = 4-C 6 H ^ 4 OSiMe 2吨卜，1 ; R = 4-C 6 H 4 Br，2；R = OC（O）氯仿2，3 ; R = OPh，4 ; R = O（2-C 6 H ^ 4森达2吨丁基），5 ]和[茹（C 2 Ò 4）（η 6 - p -cymene）{κ P -Ph通过三种不同的合成策略，从Ru（ II）芳烃前体以83-98％的产率获得了2 PO（2-C 6 H 4（SiMe 2 t Bu））}， 6。通过2-C 6 H 4 Br（OSiMe 2 t Bu）和Ph 2 PCl通过86％的收率合成了前所未有的膦Ph 2 P（O（2-C 6 H 4 SiMe 2 t Bu））。分子内氧到碳1,3的甲硅烷基迁移（retro-Brook重排）。所有的复合物完全表征通过分析和光谱学方法，

  DOI：

  10.1039/c7dt03385k
• 作为产物：
  描述：

  [chlororuthenium(II) bis(triphenylphosphane)(η6-p-cymene)] hexafluorophosphate 在 三乙胺 、 lithium chloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 [dichloro(p-cymene)(triphenylphosphane)ruthenium(II)]
  参考文献：
  名称：

  Somatostatin Subtype-2 Receptor-Targeted Metal-Based Anticancer Complexes

  摘要：

  Conjugates of a dicarba analogue of octreotide, a potent somatostatin agonist whose receptors are overexpressed on tumor cells, with [PtCl2(dap)] (dap = 1-(carboxylic acid)-1,2-diaminoethane) (3), [(eta(6)-bip)Os(4-CO2-pico)Cl] (bip = biphenyl, pico = picolinate) (4), [(eta(6)-p-cym)RuCl](dap)(+) (p-cym = p-cymene) (5), and [(eta(6)-p-cym)RuCl(imidazole-CO2H)(PPh3)](+) (6), were synthesized by using a solid-phase approach. Conjugates 3-5 readily underwent hydrolysis and DNA binding, whereas conjugate 6 was inert to ligand substitution. NMR spectroscopy and molecular dynamics calculations showed that conjugate formation does not perturb the overall peptide structure. Only 6 exhibited antiproliferative activity in human tumor cells (IC50 = 63 +/- 2 mu M in MCF-7 cells and IC50 = 26 +/- 3 mu M in DU-145 cells) with active participation of somatostatin receptors in cellular uptake. Similar cytotoxic activity was found in a normal cell line (IC50 = 45 +/- 2.6 mu M in CHO cells), which can be attributed to a similar level of expression of somatostatin subtype-2 receptor. These studies provide new insights into the effect of receptor-binding peptide conjugation on the activity of metal-based anticancer drugs, and demonstrate the potential of such hybrid compounds to target tumor cells specifically.

  DOI：

  10.1021/bc300173h
• 作为试剂：
  描述：

  1-乙炔基-2-氟苯 、 苯甲酸 在 [dichloro(p-cymene)(triphenylphosphane)ruthenium(II)] 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以35%的产率得到
  参考文献：
  名称：

  Asymmetric Hydrogenation of 1-Alkyl and 1-Aryl Vinyl Benzoates: A Broad Scope Procedure for the Highly Enantioselective Synthesis of 1-Substituted Ethyl Benzoates

  摘要：

  The enantioselective hydrogenation of enol esters of formula CH2=C(OBz)R with rhodium catalysts based on phosphine phosphite ligands (P-OP) has been studied. The reaction has a broad scope, and it is suitable for the preparation of products possessing a wide variety of R substituents. For the cases where R is a primary alkyl, high catalyst activity (S/C = 500) and enantioselectivities (95-99% ee) were obtained with a catalyst characterized by an ethane backbone and a PPh2 fragment. In contrast, for R = t-Bu, a catalyst possessing a benzene backbone provided the best results (97% ee). Derivatives with a cycloalkyl R substituent were particularly difficult substrates for this reaction. A broader catalyst screening was required for these substrates, which identified a catalyst possessing a P(m-xylyl)(2) fragment as the most appropriate one, affording enantioselectivities between 90 and 95% ee. Outstanding enantioselectivities (99% ee) and high catalyst activity (S/C = 500-1000) were also obtained in the case of substrates bearing a Ph or a fluoroaryl R substituent. In addition, the system is also appropriate for the preparation of other synthetically useful esters as those for R = benzyl, 2-phenylethyl or N-phthalimido alkyl chains. Likewise, the hydrogenation of divinyl dibenzoates proceeded with very high diastero- and enantioselectivity, generating rather low amounts of the meso isomer (3-6%). On the other hand, substrates with Br and MeO substituents at the phenyl benzoate ring, suitable for further functionalization, have also been examined. The results obtained indicate no detrimental effect of these substituents in the hydrogenation. Alternatively, the methodology has been applied to the highly enantioselective synthesis of deuterium isotopomers of 1-octyl benzoate bearing CDH2, CD2H, or CD3 fragments. Finally, as a practical advantage of the present system, it has been observed that the high performance of the catalysts is retained in highly concentrated solutions or even in the neat substrate, minimizing both the amount of solvent added and the volume of the reaction.

  DOI：

  10.1021/cs501402z

文献信息

• Phosphine ligands in the ruthenium-catalyzed reductive amination without an external hydrogen source
  作者：Maria Makarova、Oleg I. Afanasyev、Fedor Kliuev、Yulia V. Nelyubina、Maria Godovikova、Denis Chusov

  DOI：10.1016/j.jorganchem.2021.121806

  日期：2021.6

  A systematic study of the phosphine additives influence on the activity of a ruthenium catalyst in reductive amination without an external hydrogen source was carried out. [CymeneRuCl2]2 was used as a reference catalyst, and a broad set of phosphines including Alk3P, Alk2ArP, Ar3P and X3P was screened. Three complexes of general formula (Cymene)RuCl2PR3 were isolated in a pure form, and their catalytic

  在没有外部氢源的情况下，对膦添加剂对钌催化剂在还原胺化中的活性的影响进行了系统的研究。[CymeneRuCl 2 ] 2用作参考催化剂，并筛选出包括Alk 3 P，Alk 2 ArP，Ar 3 P和X 3 P在内的各种膦。以纯形式分离了三种通式（Cymene）RuCl 2 PR 3的配合物，并将其催化活性与原位进行了比较生成的复合体。发现具有电子受体基团的无阻碍的三芳基膦是最透视的活化剂，大约增加了催化剂的活性。六倍，Alk 2 ArP配体的影响较小，而三烷基膦使钌催化剂失活。
• Influence of the Linker Length on the Cytotoxicity of Homobinuclear Ruthenium(II) and Gold(I) Complexes
  作者：Lucinda K. Batchelor、Emilia Păunescu、Mylène Soudani、Rosario Scopelliti、Paul J. Dyson

  DOI：10.1021/acs.inorgchem.7b01082

  日期：2017.8.21

  the antiproliferative activity of the compounds on tumorigenic (A2780 and A2780cisR) and nontumorigenic (HEK-293) cell lines was assessed. The dinuclear ruthenium(II) complexes were considerably more cytotoxic than their mononuclear counterparts, and a correlation between the lipophilicity of the linker and the cytotoxicity was observed, whereas the cytotoxicity of the gold(I) series is independent

  双核金属配合物已经成为一类有前途的抗癌化合物，具有交联生物分子靶标的能力。在这里，我们描述了两个新颖的膦连接的双核钌（II）p系列-Cymene和gold（I）配合物，其中连接的聚（乙二醇）链的长度已得到系统地修饰。评估了多核，亲脂性和接头长度对化合物对致瘤性（A2780和A2780cisR）和非致瘤性（HEK-293）细胞系抗增殖活性的影响。双核钌（II）配合物比单核钌（II）配合物具有更高的细胞毒性，并且观察到接头的亲脂性与细胞毒性之间存在相关性，而金（I）系列的细胞毒性与这些因素无关。
• Synthesis, characterization and behavior in water/DMSO solution of Ru(II) arene complexes with bioactive carboxylates
  作者：Lorenzo Biancalana、Guido Pampaloni、Stefano Zacchini、Fabio Marchetti

  DOI：10.1016/j.jorganchem.2018.05.020

  日期：2018.8

  sequential reaction of [RuCl(μ-Cl)(η6-p-cymene)]2 with sodium salicylate and PPh3 gave [Ru(κ2O,O′-salCO2)(PPh3)(η6-p-cymene)], 5, in 70% yield. The hydride complex [Ru2Cl2(μ-Cl)(μ-H)(η6-p-cymene)2], 6, was produced in 36% yield from [RuCl(μ-Cl)(η6-p-cymene)]2 and sodium formate. An optimization of the experimental work-up allowed to isolate [RuCl(μ-Cl)(η6-p-cymene)]2 with an improved yield respect to the

  将[RuCl（μ-Cl）的（η的反应6 - p -cymene）] 2与羧酸钠，在甲醇或乙腈溶液，得到复合物将[RuCl（κ 2 ö -RCO 2）（η 6 - p -cymene ）]（RCO 2  =丙戊酸盐，1；阿司匹林，2；双氯芬酸，3），收率79-96％。类似地，将[RuCl（κ 2 ö -dfCO 2）（η 6 -苯）]，4，在混合副产物将[RuCl（μ-Cl）的（η获得具有轻微的6 -苯）] 2和双氯芬酸钠/银。将[RuCl（μ-Cl）的（η的连续反应6 - p -cymene）] 2与水杨酸钠和PPH 3得到的[Ru（κ 2 ö，O' -salCO 2）（PPH 3）（η 6 - p -cymene）]，5，收率70％。的氢化物络合物的[Ru 2氯2（μ-Cl）的（μ-H）（η 6 - p -cymene）2 ]，6，在从产率将[RuCl（μ-Cl）的（η36％制备6 - p
• A Mild One-Pot Reduction of Phosphine(V) Oxides Affording Phosphines(III) and Their Metal Catalysts
  作者：Łukasz Kapuśniak、Philipp N. Plessow、Damian Trzybiński、Krzysztof Woźniak、Peter Hofmann、Phillip Iain Jolly

  DOI：10.1021/acs.organomet.0c00788

  日期：2021.3.22

  metal-free reduction of a range of phosphine(V) oxides employing oxalyl chloride as an activating agent and hexachlorodisilane as reducing reagent has been achieved under mild reaction conditions. The method was successfully applied to the reduction of industrial waste byproduct triphenylphosphine(V) oxide, closing the phosphorus cycle to cleanly regenerate triphenylphosphine(III). Mechanistic studies and quantum

  在温和的反应条件下，已经实现了使用草酰氯作为活化剂和六氯乙硅烷作为还原剂的一系列膦（V）氧化物的无金属还原。该方法成功地用于减少工业废物副产物三苯基膦（V）的氧化，关闭磷循环以干净地再生三苯基膦（III）。机理研究和量子化学计算支持中间体phospho盐的离解氯离子对乙硅烷硅的攻击，这是脱保护的限速步骤。
• Ruthenium-Stabilized Low-Coordinate Phosphorus Atoms. <i>p</i>-Cymene Ligand as Reactivity Switch
  作者：Richard Menye-Biyogo、Fabien Delpech、Annie Castel、Véronique Pimienta、Heinz Gornitzka、Pierre Rivière

  DOI：10.1021/om7004854

  日期：2007.9.1

  structural and spectroscopic features and of the reactivity of ruthenium phosphinidene complexes (η6-Ar)(PCy3)Ru(PMes*) (2a, Ar = p-cymene; 2b, Ar = benzene) has been undertaken. The structures of complexes 2a and 2b have been determined by single-crystal X-ray diffraction and display similar features. Both compounds possess identical chemical behavior toward Brönsted acids such as HBF4:  protonation of the

  的结构和光谱特征和钌亚膦络合物的反应性（η的详细比较研究6 -Ar）（PCY 3）的Ru（机动设备*）（图2a中，Ar = p -cymene;图2b中，Ar =苯）一直承担。配合物2a和2b的结构已经通过单晶X射线衍射确定并显示出相似的特征。这两种化合物具有朝向相同的布朗斯台德化学行为酸如HBF 4：的亚膦的质子化配位体产生了新的阳离子络合物[（η 6 -Ar）（PCY 3）的Ru（PHMes *）] BF 4（3aBF4，Ar ＝ p-胞嘧啶；3bBF 4，Ar =苯），它具有前所未有的含磷氢取代基。已经使用X射线衍射技术表征了3aBF 4。的孤对配体亚膦遗体还向路易斯酸BH访问的磷原子的3：的反应图2a和2b中与硼烷，得到加合物（η 6 -Ar）（PCY 3）的Ru [P（BH 3）的Mes *]（ 4a，Ar =对甲基苯甲基； 4b，Ar =苯）。在更大的硼烷BPh 3存在下直到将