[RuCl(PCy3)(p-cymene)]OTf | 223905-01-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: [RuCl(PCy3)(p-cymene)]OTf
• 英文别名: (η6-p-cymene)Ru(P(cyclohexyl)3)Cl triflate；[(η6-p-cymene)RuCl(PCy3)][OTf]；Ru(η6-p-cymene)Cl(PCy3)(OTf)；[(η6-p-cymene)RuCl(PCy3)]OTf；[RuCl(P(C6H11)3)(p-cymene)]CF3SO3；Ru(Cl)(PCy3)(p-cymene) CF3SO3；Chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene;tricyclohexylphosphane;trifluoromethanesulfonate
• CAS: 223905-01-9；1016161-08-2
• 化学式: CF₃O₃S*C₂₈H₄₇ClPRu
• 分子量: 700.248
• InChiKey: KNACNNOPRLBIQG-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  10.32
• 重原子数：
  39
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  65.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [RuCl(PCy3)(p-cymene)]OTf 、 1,1-双(4-甲氧基苯基)-2-丙炔-1-醇 以 氘代苯 为溶剂， 生成 (η6-p-cymene)Ru(P(cyclohexyl)3)(CCC(p-OCH3-C6H4)2)Cl triflate
  参考文献：
  名称：

  阳离子对-Cymene钌（II）配合物中的亚烯基至茚基重排：溶剂，抗衡阴离子和取代基的作用是催化烯烃复分解的关键步骤

  摘要：

  [（η的反应6 - p的RuCl（PCY -cymene）3 [光学传递函数]的Ph）] 2 C（OH）C≡CH，在苯室温d 6或在二氯甲烷- d 2，，得到allenylidene复杂[（η 6 - p -cymene）的RuCl（═C═C═CPh 2）PCY 3 ] [光学传递函数（{4A} ），它是用来在原位作为用于闭环复分解（RCM）的催化剂的反应二烯丙基糖基酰胺。通过1 H NMR光谱在苯-d 6和二氯甲烷-d 2中进行动力学研究。烯烃复分解过程的速率随钌络合物的浓度增加而增加，但由于决定亚烯基络合物的转化率而与烯烃浓度无关。苯-d 6中的TOF值高于二氯甲烷-d 2中的TOF值。所述allenylidene复合物的自发或热诱导转化[（η 6 - p -cymene）的RuCl（═C═C═CAr 2）PR 3 ] [X]（AR =苯基，X = CF 3 SO 3 -（OTF） （{

  DOI：

  10.1021/om100654z
• 作为产物：
  描述：

  对异丙苯基三环己基磷二氯化钌 、 silver trifluoromethanesulfonate 以 二氯甲烷 为溶剂， 以95%的产率得到[RuCl(PCy3)(p-cymene)]OTf
  参考文献：
  名称：

  Room temperature operating allenylidene precatalyst [LnRuξCξCξCR2]+X- for olefin metathesis: dramatic influence of the counter anion X-

  摘要：

  亚荃钌(II)配合物[(对亚甲基)(PCy3)Cl- RuξCξCξCPh2]+X-, 2a, (X-=CF3SO3-)，是由市售的[RuCl2(对亚甲基)]2 通过一次反应生成的、室温下催化 N,N-二烯丙基对甲苯磺酰胺的闭环偏析，而 2b（X-=BF4-）则有利于 1,6-二烯 3 环化成五元杂环 5，且不损失原子。在 2b 中加入 BF3Â-OEt2 可以恢复其在 RCM 反应中的选择性。催化剂 2a 还能促进烯炔 6 的偏合成反应，生成 3-乙烯基-2,5-二氢呋喃 7。

  DOI：

  10.1039/a808859d
• 作为试剂：
  描述：

  三乙基矽乙炔 在 [RuCl(PCy3)(p-cymene)]OTf 、 2-vinyl-1,3,2-dioxaborinane 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 18.0h， 生成 triethyl(4-triethylsilylbut-1-en-3-ynyl)silane
  参考文献：
  名称：

  一种新的催化途径，用于取代硼烷基和硼烷基甲硅烷基的buta-1,3-二烯。

  摘要：

  乙烯基取代的硼酸酯在含有Ru-H键的配合物（最好是[Ru（CO）ClH（PCy（3））（2），Cy：环己基）的存在下，与末端乙炔（涉及甲硅烷基乙炔）发生区域选择性反应，尽管与除了苯基乙炔以外，可生产出硼烷基和硼烷基甲硅烷基取代的buta-1,3-二烯，优选E，E-二烯。该反应为制备二烯基硼酸酯，特别是二烯基甲硅烷基硼酸酯开辟了一条新的催化路线，所述二烯基硼酸酯是有机和天然产物合成中的功能化构造单元。事实证明，这种新反应的机理包括将炔烃插入Ru-H键中，然后将配位的硼酸乙烯基酯插入Ru-C =键中，然后将β-氢转移到金属上，从而消除硼基二烯或硼基甲硅烷基二烯。

  DOI：

  10.1002/chem.200800518

文献信息

• Fluorine-containing α-alkynyl amino esters and access to a new family of 3,4-dehydroproline analogues
  作者：David Se´meril、Je´rôme Le Nôtre、Christian Bruneau、Pierre H. Dixneuf、Alexey F. Kolomiets、Sergey N. Osipov

  DOI：10.1039/b007396m

  日期：——

  New α-alkynyl, α-CF3 amino esters have been prepared from electrophilic imines and used to produce 3-alkenyl-3,4-dehydroproline derivatives, ia enyne metathesis with the precatalyst [RuCCCPh2(Cl)(PCy3)(arene)]O3SCF3. These new conjugated fluorine-containing dienes are active substrates for the Diels–Alder reaction and lead to a new class of bicyclic amino esters.

  新型α-炔基和α-CF3氨基酯已从电亲核亚胺合成，并用于通过与前催化剂[RuCCCPh2(Cl)(PCy3)(arene)]O3SCF3的炔烯复分解反应生成3-烯基-3,4-脱氢脯氨酸衍生物。这些新的含氟共轭二烯是Diels–Alder反应的活性底物，并导致一种新的双环氨基酯类别的形成。
• Rate Studies and Mechanism of Ring-Closing Olefin Metathesis Catalyzed by Cationic Ruthenium Allenylidene Arene Complexes
  作者：Mauro Bassetti、Fabio Centola、David Sémeril、Christian Bruneau、Pierre H. Dixneuf

  DOI：10.1021/om030497w

  日期：2003.10.1

  The ring-closing metathesis reaction of N,N-diallyltosylamide (2) catalyzed by [(eta(6)-p-cymene)(PCy3)RuCl(=C=C=CPh2)]X (X = OTf (CF3SO3) (1), PF6, BF4, SbF6) and by [(eta(6)-p- cymene)(PCy3)RuCl(=C=C=C(p-Y-C6H4)(2)]OTf (Y = MeO, Cl, F) complexes has been monitored in situ by H-1 NMR, in benzene-d(6) and in dichloromethane-d(2), in the temperature range 33-58 degreesC. The reaction proceeds selectively to form N-tosyl-2,5-dihydropyrrole (3), in the case of complexes [(eta(6)-p-cymene)(PCy3)RuCl(=C=C=CPh2)]X (X = OTf, PF6), under thermal activation, while lower reactivity and selectivity are exhibited by the other complexes. Evidence is given for an activation step leading to the catalytic species. Under pseudo-first-order conditions, the metathesis reaction catalyzed by complex 1 is first-order in the diallylic substrate in benzene-d(6) above 50 degreesC when the propagation step is slower than the activation of the catalytic species. The reaction is zero-order in substrate at lower temperatures when the activation of the ruthenium complex is slower than the ring-closing metathesis process and faster in benzene-d(6) than in dichloromethane-d(2). The presence of added p-cymene does not inhibit the reactivity, while inhibition occurs in the presence of added PCy3. In the latter case, the substrate is converted slowly into an isomeric product. When appropriate, the behavior of complex 1 as precatatyst is compared with that of other catalytic systems. H-1 NMR, FT-IR, and UV-visible analyses indicate that the activation process of complex 1 is characterized by an intramolecular transformation of the ruthenium-allenylidene group into the corresponding ruthenium-phenylindenylidene moiety.
• Alkenylcarbene Ruthenium Arene Complexes as Initiators of Alkene Metathesis: An Enyne Creates a Catalyst that Promotes Its Selective Transformation
  作者：Ricardo Castarlenas、Matthieu Eckert、Pierre H. Dixneuf

  DOI：10.1002/anie.200462865

  日期：2005.4.22
• Allenylidene-to-Indenylidene Rearrangement in Arene−Ruthenium Complexes: A Key Step to Highly Active Catalysts for Olefin Metathesis Reactions
  作者：Ricardo Castarlenas、Chloé Vovard、Cédric Fischmeister、Pierre H. Dixneuf

  DOI：10.1021/ja0579762

  日期：2006.3.1

  The allenyliclene-ruthenium complexes [(eta(6)-arene)RuCl(=C=C=CR2)(PR'(3))]OTf (R-2 = Ph; fluorene, Ph, Me; PR'3 = PCY3, (PPr3)-Pr-i, PPh3) (OTf = CF3SO3) on protonation with HOTf at -40 degrees C are completely transformed into alkenylcarbyne complexes [(eta(6)-p-cymene)RuCl( CCH=CR2)(PR3)](OTf)(2). At -20 degrees C the latter undergo intramolecular rearrangement of the allenylidene ligand, with release of HOTf, into the indenylidene group in derivatives [(eta(6)-arene)RuCl(indenylidene)(PR3)]OTf. The in situ-prepared indenylidene- ruthenium complexes are efficient catalyst precursors for ring-opening metathesis polymerization of cyclooctene and cyclopentene, reaching turnover frequencies of nearly 300 s(-1) at room temperature. Isolation of these derivatives improves catalytic activity for the ring-closing metathesis of a variety of dienes and enynes. A mechanism based on the initial release of arene ligand and the in situ generation of the active catalytic species RuCI(OTf)(=CH2)(PR3) is proposed.
• Allenylidene-ruthenium-arene precatalyst for ring opening metathesis polymerisation (ROMP)
  作者：Ricardo Castarlenas、David Sémeril、Alfred F. Noels、Albert Demonceau、Pierre H. Dixneuf

  DOI：10.1016/s0022-328x(02)01880-6

  日期：2002.12

  The ruthenium allenylidene complex [RuCl(=C=C=CPh2)(PCy3)(P-cymene)][OTf] constitutes an excellent precatalyst for the ROMP at room temperature of norbornene (M-n = 198 X 10(3), PDI = 1.8) and cyclooctene (M-n = 143 x 10(3), PDI = 1.9). The activation of the precatalyst by initial heating (25 min, 60 degreesC) generates a catalytic species that operates at room temperature to produce in 10 min 90% of polyoctenamer (M-n = 151 x 10(3), PDI = 1.7). (C) 2002 Elsevier Science B.V. All rights reserved.