[(η(6)-cymene)RuCl2(η(1)-Ph2PCH2P(O)Ph2)] | 240803-86-5

• 英文名称: [(η(6)-cymene)RuCl2(η(1)-Ph2PCH2P(O)Ph2)]
• 英文别名: [(η6-p-cymeme)RuCl2(η1-PPh2CH2POPh2)]；[(η6-p-cymene)RuCl2(η1-dppmO)]
• CAS: 240803-86-5
• 化学式: C₃₅H₃₆Cl₂OP₂Ru
• 分子量: 706.594
• InChiKey: UZJBSDGJRWXHCW-UHFFFAOYSA-L

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：

  silver hexafluoroantimonate 、 [(η(6)-cymene)RuCl2(η(1)-Ph2PCH2P(O)Ph2)] 以 二氯甲烷 为溶剂， 以88%的产率得到[(η(6)-cymene)RuCl(η(2)-Ph2PCH2P(O)Ph2)][SbF6]
  参考文献：
  名称：

  Diastereoselectivity in Chiral Ruthenium Complexes of Bidentate Bisphosphine Monoxide Ligands:  Controlling Epimerization in Aldehyde Complexes and 16-Electron Intermediates

  摘要：

  Heterobidentate and hemilabile ligands involving P,O-donor chelates produce chiral metal centers when bound to arene-ruthenium complexes. This chirality in cymene complexes produces diastereotopic methyl groups in the isopropyl ligand which serve as a detector of the chirality at the metal. [CyRu(eta(2)-chelate-P,O)Cl](+) cations are precursors to strong 16-electron dicationic Lewis acids which have potential use in asymmetric catalysis. Sixteen-electron complexes of this type, however, provide a pathway with a low barrier to racemization or epimerization of the metal center in intermediates, such as [CyRu(eta(2)-chelate-P,O)(PhCHO)](2+). Substitution of the central carbon in diphenylphosphinomethane monoxide (dppmO) forces the ligand to adopt a configuration with the substituent in an endo position, thus forcing the 16-electron intermediate to return diastereoselectively to its original configuration and prevents epimerization. Thus, an X-ray structure shows that; (R-Ru*,R-C*)[CyRu(eta(2)- Ph2PCHR)Ph2PO-P,O)Cl](+) is the preferred diastereomeric pair. In the parent, [CyRu(eta(2)-dppmO-P,O)(ligand)](2+), racemization occurs at the metal center, since there is nothing driving the preferential formation of either the R or S ruthenium center. When the ligands are chiral, however, the metal center epimerizes to minimize steric interactions in the two diastereomers. The equilibrium between [(R-Ru)-CyRu(eta(2)-dppmO-P,O)(R-C-ligand)](2+) and [(S-Ru)-CyRu(eta(2)-dppmO-P,O)(R-C-ligand)](2+) reflects a 37% de for (1R)-(-)-myrtenal. Since a substituent on the central carbon prevents epimerization at the metal center, this diastereoselectivity is reflected in a preference for binding of (R-C)-ligand by either [(R-Ru,R-C)CyRu(eta(2)-Ph2PCHPr)Ph2PO-P,O)](2+) or [(S-Ru,S-C)-CyRu(eta(2)-Ph2PCHPr)Ph2PO-P,O)](2+). An X-ray structure of rac-[(R-Ru*,R-C)-CyRu(eta(2)-Ph2PCHPr)Ph2PO-P,O)(PhCHO](2+) shows that the aldehyde assumes an orientation that would suggest one stereoface of the aldehyde may be more susceptible to attack.

  DOI：

  10.1021/om981053g
• 作为产物：
  描述：

  [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 、 双二苯基膦基甲基二苯基氧化膦 以 二氯甲烷 为溶剂， 以99%的产率得到[(η(6)-cymene)RuCl2(η(1)-Ph2PCH2P(O)Ph2)]
  参考文献：
  名称：

  Diastereoselectivity in Chiral Ruthenium Complexes of Bidentate Bisphosphine Monoxide Ligands:  Controlling Epimerization in Aldehyde Complexes and 16-Electron Intermediates

  摘要：

  Heterobidentate and hemilabile ligands involving P,O-donor chelates produce chiral metal centers when bound to arene-ruthenium complexes. This chirality in cymene complexes produces diastereotopic methyl groups in the isopropyl ligand which serve as a detector of the chirality at the metal. [CyRu(eta(2)-chelate-P,O)Cl](+) cations are precursors to strong 16-electron dicationic Lewis acids which have potential use in asymmetric catalysis. Sixteen-electron complexes of this type, however, provide a pathway with a low barrier to racemization or epimerization of the metal center in intermediates, such as [CyRu(eta(2)-chelate-P,O)(PhCHO)](2+). Substitution of the central carbon in diphenylphosphinomethane monoxide (dppmO) forces the ligand to adopt a configuration with the substituent in an endo position, thus forcing the 16-electron intermediate to return diastereoselectively to its original configuration and prevents epimerization. Thus, an X-ray structure shows that; (R-Ru*,R-C*)[CyRu(eta(2)- Ph2PCHR)Ph2PO-P,O)Cl](+) is the preferred diastereomeric pair. In the parent, [CyRu(eta(2)-dppmO-P,O)(ligand)](2+), racemization occurs at the metal center, since there is nothing driving the preferential formation of either the R or S ruthenium center. When the ligands are chiral, however, the metal center epimerizes to minimize steric interactions in the two diastereomers. The equilibrium between [(R-Ru)-CyRu(eta(2)-dppmO-P,O)(R-C-ligand)](2+) and [(S-Ru)-CyRu(eta(2)-dppmO-P,O)(R-C-ligand)](2+) reflects a 37% de for (1R)-(-)-myrtenal. Since a substituent on the central carbon prevents epimerization at the metal center, this diastereoselectivity is reflected in a preference for binding of (R-C)-ligand by either [(R-Ru,R-C)CyRu(eta(2)-Ph2PCHPr)Ph2PO-P,O)](2+) or [(S-Ru,S-C)-CyRu(eta(2)-Ph2PCHPr)Ph2PO-P,O)](2+). An X-ray structure of rac-[(R-Ru*,R-C)-CyRu(eta(2)-Ph2PCHPr)Ph2PO-P,O)(PhCHO](2+) shows that the aldehyde assumes an orientation that would suggest one stereoface of the aldehyde may be more susceptible to attack.

  DOI：

  10.1021/om981053g

文献信息

• The Synthesis and Characterisation of Bis(phosphane)‐Linked ( ⁶ ‐ <i>p</i> ‐Cymene)ruthenium( <scp>II</scp> )–Borane Compounds
  作者：Adrian B. Chaplin、Rosario Scopelliti、Paul J. Dyson

  DOI：10.1002/ejic.200500706

  日期：2005.12

  where the dppa bridges two ruthenium centres, and uncoordinated phosphane; the bridging species was also structurally characterised in the solid state. In contrast, the reaction of [(η6-p-cymene)RuCl2(PPh3)] with dppa in the presence of [NH4]PF6 results in the formation of [(η6-p-cymene)RuCl(PPh3)(η1-dppa)]PF6, which is stable in solution. A series of linked ruthenium-borane complexes, viz. [(η6-p-

  已经研究了 [(η6-p-cymene)RuCl2]2 与一些双（磷烷）配体（dppm、dppe、dppv、dppa、dpp14b、dppf）的反应。通常，获得了产物的混合物，尽管悬垂的磷烷配合物 [(η6-p-cymene)RuCl2(η1-dppv)] 和 [(η6-p-cymene)RuCl2(η1-dppa)] 在X 射线衍射测定为固态。后一种复合物以较低的产率获得，并进行平衡反应，导致形成二聚体，其中 dppa 桥接两个钌中心和未配位的磷烷；桥接物质在固态下也具有结构特征。相反，在 [NH4]PF6 存在下，[(η6-p-cymene)RuCl2(PPh3)] 与 dppa 的反应导致形成 [(η6-p-cymene)RuCl(PPh3)(η1-dppa )]PF6，在溶液中稳定。一系列连接的钌硼烷配合物，即。[(η6-p-cymene)RuCl2(η1-phosphane-BH3)]
• Arene displacement, C–H activation and acetonitrile insertion reactions enabled by coordination of a functionalized iminophosphorane to a RuII–p-cymene scaffold
  作者：Rani Gourkhede、Bhupinder Kaur、Basvaraj S. Kote、Maravanji S. Balakrishna

  DOI：10.1039/d4dt00940a

  日期：——

  activation, tethered η6-arene coordination, ortho-metallation or PN bond cleavage/rearrangement reactions. Interestingly, a similar reaction in CH3CN in the presence of AgBF4 resulted in the insertion of CH3CN into the PN bond to form a novel metallacycle [Ru(NCMe)3(PC2PN(CH3)CNAr*)-κ3-N,N,P}][BF4]2 (5) containing 4- and 5-membered rings via an aza-Wittig type reaction. Complex 4 showed very good catalytic

  空间要求较高的亚氨基正膦 (Ph 2 PCH 2 Ph 2 P) 的反应 NAr*（此处称为 PCPNAr*；Ar* = 2,6-二苯甲基-4-甲基苯基），( 1 ) 与 [Ru(η 6 - p -伞花烃)Cl 2 ] 2产生三种不同类型的络合物， [RuCl 2 (η 6 - p -伞花烃)(PCPNAr*)-κ 1 - P }] ( 2 ), [RuCl(P(O)CPNAr*)(κ 2 - N , C )( C -η 6-芳烃)}] ( 3 ) 和 [RuCl(POCP NAr*)(κ 2 - N , Co )( C -η 6 -芳烃)}] ( 4 )，取决于通过CH 活化、束缚 η 6 -芳烃配位、邻位金属化或 P 的反应条件 N键断裂/重排反应。 有趣的是，在 AgBF 4存在下，CH 3 CN 中发生类似反应，导致 CH 3 CN 插入到 P 中。 N键形成新型金属环[Ru(NCMe)
• Catalytic Nitrile Hydration with [Ru(η⁶-<i>p</i>-cymene)Cl₂(PR₂R′)] Complexes: Secondary Coordination Sphere Effects with Phosphine Oxide and Phosphinite Ligands
  作者：Spring Melody M. Knapp、Tobias J. Sherbow、Robert B. Yelle、J. Jerrick Juliette、David R. Tyler

  DOI：10.1021/om400380j

  日期：2013.7.8

  The rates of nitrile hydration reactions were investigated using [Ru(eta(6)-p-cymene)Cl-2(PR2R')] complexes as homogeneous catalysts, where PR2R' = PMe2(CH2P(O)Me-2), PMe2(CH2CH2P(O)Me-2), PPh2(CH2P(O)Ph-2), PPh2(CH2CH2P(O)Ph-2), PMe2OH, P(OEt)(2)OH. These catalysts were studied because the rate of the nitrile-to-amide,, hydration reacfion was hypothesized to be affected by the position of the io., hydrogen bond accepting group in the secondary coordination sphere of the catalyst. Experiments showed that, the rate of nitrile hydration was fastest when using [Ru(eta(6)-p-cymene)Cl2PMe2OH]: i.e., the catalyst with the hydrogen bond accepting group capable of forming the most stable ring in the transition state of the rate-limiting step. This catalyst is also active at pH 3.5. and at low temperatures-conditions where alpha-hydroxynitriles (cyanohydrins produce less cyanide, a known poison for organometallic nitrile hydration catalysts. The [Ru(eta(6)-p-cymene)Cl2PMe2OH] catalyst completely converts the cyanohydrins glycolonitrile, and, lactonitrile to their corresponding alpha-hydroxyamides faster than previously investigated Catalysts. [Ru(eta(6)-p-cymene)Cl2PMe2OH] is not, however, a good catalyst for acetone cyanohydrin hydration, because it is susceptible to cyanide poisoning. Protecting the -OH group of acetone cyanohydrin was shown to be an effective way to prevent cyanide poisoning, resulting in quantitative hydration of acetone cyanohydrin acetate.