Ru(CO)2(PPh3)2(O2CPh)2 | 128239-19-0

• 英文名称: Ru(CO)2(PPh3)2(O2CPh)2
• 英文别名: [Ru(κ1-O2CPh)2(PPh3)2(CO)2]
• CAS: 128239-19-0
• 化学式: C₅₂H₄₀O₆P₂Ru
• 分子量: 923.904
• InChiKey: MLNLVZAMBGAUJY-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

• 作为产物：
  描述：

  一氧化碳 、 cis-[Ru(κ2-O2CPh)2(PPh3)2] 在 AgBF₄ 作用下， 以 二氯甲烷 为溶剂， 生成 Ru(CO)2(PPh3)2(O2CPh)2
  参考文献：
  名称：

  Ruthenium carboxylate complexes as easily prepared and efficient catalysts for the synthesis of β-oxopropyl esters

  摘要：

  The easily prepared complex cis-[Ru(kappa(2)-O2CMe)(2)(PPh3)(2)] is an effective catalyst for the addition of carboxylic acids to propargyl alcohols to afford beta-oxopropyl esters. The reaction is tolerant to a range of functional groups on the propargyl alcohol and is effective in the case of the steroid ethisterone. An investigation into the ruthenium-containing products from the reaction involving benzoic acid revealed that rapid exchange between coordinated acetate and benzoate ligands occurs. The synthesis of crystallographically characterised cis-[Ru(kappa(2)-O2CPh)(2)(PPh3)(2)] was developed. This benzoate-substituted complex was shown to react with HC CPh and HC CC(OH)PhH to give [Ru(kappa(2)-O2CPh)(kappa(1)-O2CPh)(=C=CPhH) (PPh3)(2)] and [Ru(kappa(2)-O2CPh)(kappa(1)-O2CPh)(=C=CC{OH}PhH)(PPh3)(2)] respectively. Reaction of cis-[Ru(kappa(2)-O2CPh) (2)(PPh3)(2)] with CO affords [Ru(kappa(2)-O2CPh)(kappa(1)-O2CPh)(CO)(PPh3)(2)] or [Ru(kappa(2)-O2CPh)(2)(CO)(2)(PPh3)(2)] depending on the conditions employed. Related carbonyl compounds are thought to be the rutheniumcontaining products from the catalytic reactions and [Ru(kappa(2)-O2CMe)(kappa(1)-O2CMe)(CO)(PPh3)(2)] was also shown to be a competent catalyst. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2010.10.001

文献信息

• Ruthenium Carboxylate Complexes as Efficient Catalysts for the Addition of Carboxylic Acids to Propargylic Alcohols
  作者：Janine Jeschke、Christian Gäbler、Marcus Korb、Tobias Rüffer、Heinrich Lang

  DOI：10.1002/ejic.201500203

  日期：2015.6

  Heinrich Lang at the Technische Universitat Chemnitz, Germany. The cover image shows the atom-economical and highly selective addition of carboxylic acids to propargylic alcohols to give β-oxopropyl esters. This conversion is catalyzed by ruthenium complexes, represented by the skater in our picture.

  德国开姆尼茨理工大学的 Heinrich Lang 小组受邀为本期杂志封面。封面图片显示了羧酸与炔丙醇的原子经济性和高选择性加成，以得到 β-氧代丙酯。这种转化由钌配合物催化，由我们图片中的溜冰者代表。
• Atom Economic Ruthenium-Catalyzed Synthesis of Bulky β-Oxo Esters
  作者：Janine Jeschke、Marcus Korb、Tobias Rüffer、Christian Gäbler、Heinrich Lang

  DOI：10.1002/adsc.201500712

  日期：2015.12.14

  Ruthenium complexes with the formulae Ru(CO)2(PR3)2(O2CPh)2 [6a–h; R=n-Bu, p-MeO-C6H4, p-Me-C6H4, Ph, p-Cl-C6H4, m-Cl-C6H4, p-CF3-C6H4, m,m′-(CF3)2C6H3] were prepared by treatment of triruthenium dodecacarbonyl [Ru3(CO)12] with the respective phosphine and benzoic acid or by the conversion of Ru(CO)3(PR3)2 (8e–h) with benzoic acid. During the preparation of 8, ruthenium hydride complexes of type Ru(CO)(PR3)3(H)2

  钌配合物，分子式为Ru（CO）2（PR 3）2（O 2 CPh）2 [ 6a – h ; R ＝n- Bu，p -MeO-C 6 H 4，p -Me-C 6 H 4，Ph，p -Cl-C 6 H 4，m -Cl-C 6 H 4，p -CF 3 -C 6 H 4，m，m' -（CF 3）2 C 6 H 3 ]的制备方法是用膦和苯甲酸分别处理十二碳三钌[Ru 3（CO）12 ]或将Ru（CO）3（PR 3）2（8e - h）转化为苯甲酸。在制备8的过程中，可以分离出Ru（CO）（PR 3）3（H）2（9g，h）类型的氢化钌配合物作为副产物。讨论了新合成的固态配合物的分子结构。化合物发现6a - h是将羧酸添加到炔丙醇中以生成有价值的β-氧代酯的高效催化剂。催化剂筛选显示出膦的电子性质对所得活性的显着影响。使用具有吸电子膦配体的配合物6g和6h获得了最佳性能。另外，催化剂6g在空间上需要的底物的
• Addition of carboxylic acids to alkynes catalysed by ruthenium complexes
  作者：Michal Rotem、Youval Shvo

  DOI：10.1016/0022-328x(93)80084-o

  日期：1993.4

  [Ru(PhCOO)(CO)2(PhCOOH)]2, the catalyst, indicates that the active catalytic species are mononuclear ruthenium complexes. A stoichiometric reaction modelled on the catalytic reaction was monitored by infrared spectroscopy and finally quenched with PPh3. The quenching products were identified as new mononuclear ruthenium complexes, and these identifications greatly facilitated understanding of the mechanism leading

  已经发现，通过Ru 3（CO）12以及具有一般结构[Ru（RCOO）（CO）2（L）] 12的二聚羧酸钌钌配合物可以催化向炔烃中添加羧酸。反应产生乙烯基酯。发现对于酸和炔烃都是通用的。在与苯基乙炔的反应中也形成了重排的区域异构体乙烯基酯。已经观察到羧酸的立体特异性动力学控制的顺式加成至三键。不对称炔烃的区域选择性很差。观察到相对于[Ru（PhCOO）（CO）2（PhCOOH）] 2的1/2反应阶数催化剂表示活性催化物质是单核钌络合物。通过红外光谱法监测以催化反应为模型的化学计量反应，最后用PPh 3淬灭。淬灭产物被鉴定为新的单核钌配合物，并且这些鉴定极大地促进了对导致建议的催化循环的机理的理解。
• X-ray crystal structure determination of (PhCOO)2(PPh3)2(CO)2Ru. Stereochemistry assignments
  作者：M. Rotem、Z. Stein、Y. Shvo

  DOI：10.1016/0022-328x(90)87303-u

  日期：1990.4

  (PhCOO)2(PPh3)2(CO)2Ru (1) and (p-MeC6H4COO)2(PPh3)2(CO)2Ru (2) have been made by treating tricarbonylbis(triphenylphosphine)ruthenium(0) with benzoic and p-toluic acid, respectively. An X-ray diffraction study of 1 has revealed an octahedral geometry with trans disposition of the phosphine ligands and cis disposition of the carbonyl ligands. The same stereochemistry is assigned to complex 2 and to

  配合物（PhCOO）2（PPh 3）2（CO）2 Ru（1）和（p -MeC 6 H 4 COO）2（PPh 3）2（CO）2 Ru（2）是通过处理三羰基双（三苯基膦）钌（0）分别与苯甲酸和对甲苯甲酸。的X射线衍射研究1已揭示了与八面体几何形状的反式的膦配位体和处置顺羰基配体的位置。相同的立体化学被分配给络合物2和先前报道的几种相关的络合物。这种立体化学分配澄清了文献中的一些矛盾陈述。