cis,fac-RuCl2(CO)(dimethyl sulfoxide) | 166760-43-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 亚砜
• 英文名称: cis,fac-RuCl2(CO)(dimethyl sulfoxide)
• 英文别名: fac-Ru(CO)3(DMSO)Cl2；fac-RuCl₂(CO)₃(dmso−O)；Carbon monoxide;methylsulfinylmethane;ruthenium(2+);dichloride
• CAS: 166760-43-6；288324-97-0
• 化学式: C₅H₆Cl₂O₄RuS
• 分子量: 334.142
• InChiKey: FRGQSYOTWAVXJT-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -6.11
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  39.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  cis,fac-RuCl2(CO)(dimethyl sulfoxide) 在 1,3,5-三氮杂-7-磷杂金刚烷 作用下， 以 水 为溶剂， 反应 1.0h， 生成 十二羰基三钌
  参考文献：
  名称：

  水溶性钌（II）羰基与1,3,5-Triaza-7-磷金刚烷。

  摘要：

  通过在配位领域中引入高度水溶性的1,3,5-三氮杂-7-磷金刚烷（PTA）支撑配体，我们制备具有改善的水溶性的新Ru（II）前体的策略的延续，在这项工作中，我们讨论了Ru（II）-PTA羰基化合物的很大程度上未开发的制备方法。使用了两种互补的合成方法：（1）处理一系列通式为RuCl2（CO）n（dmso）4- n的中性Ru（II）-CO-dmso化合物（n = 1-3，1-5 ）与PTA；（2）Ru（II）-PTA配合物与CO的反应。通过第一种方法，我们获得并充分表征了每个Ru原子带有一个至三个PTA配体的七个新型中性化合物，即四个单羰基，顺式，顺式，反式RuCl2（CO）（dmso-S）（PTA）2（6），反式RuCl2（CO）（PTA）3（7），顺式，mer-RuCl2（CO）（PTA）3（8），反式，反式，反式RuCl2（CO）（OH2）（PTA）2（10）和三个二羰基，反式，反式，

  DOI：

  10.1021/acs.inorgchem.8b00698
• 作为产物：
  描述：

  一氧化碳 、 cis-dichlorotetrakis(diemethylsulfoxide) ruthenium(II) 100.0 ℃ 、4.05 MPa 条件下， 反应 8.0h， 以80%的产率得到cis,fac-RuCl2(CO)(dimethyl sulfoxide)
  参考文献：
  名称：

  新型阳离子和中性Ru（II）-和Os（II）-dmso羰基化合物

  摘要：

  报道了三种阳离子Ru（II）-dmso羰基化合物以及四种中性单-和二羰基Os（II）-dmso衍生物的制备和结构表征。两个单羰基物质fac- [Ru（CO）（dmso-O）3（dmso-S）2 ] [PF 6 ] 2（11）和cis，cis，cis- [RuCl（CO）（dmso-O）2（dmso-S）2 ] [PF 6 ]（12）是从中性单羰基前体顺式，反式，顺式-[RuCl 2（CO）（dmso-O）（dmso-S）2制备的。]（3）用dmso逐步替换氯化物时，dmso分别通过氧原子结合。在中性三羰基前体fac- [RuCl ]处理后，获得了二羰基阳离子络合物顺式，顺式，反式-[Ru（CO）2（dmso-O）2（dmso-S）Cl] [PF 6 ]（PF 6）（13）。在存在DMSO的情况下用AgPF 6取代2（CO）3（dmso-O）]（8）：用dmso-O取代Cl –也暗示另一种d

  DOI：

  10.1021/ic401940z

文献信息

• The Insertion of Ruthenium into Porphyrins Revisited and Improved: Proof of Concept Results with a Ruthenium(II) Monocarbonyl Compound, and the Spectacular Effect of Propionic Acid
  作者：Alessio Vidal、Federica Battistin、Elisabetta Iengo、Barbara Milani、Enzo Alessio

  DOI：10.1002/ejic.201900428

  日期：2019.6.30

  second example that uses a RuII carbonyl for porphyrin ruthenation, the first one having been reported almost 50 years ago and then neglected. From a practical point of view, we show the spectacular effect of propionic acid as solvent for performing the ruthenation of neutral and anionic model porphyrins with Ru3(CO)12 (1). This process turned out to be extremely efficient and advantageous in terms of

  这一贡献解决了Ru II -CO片段在模型卟啉中的插入（即钌化）的问题，具有Janus的特性，具有投机性和实用性。作为概念证明，我们证明了使用Ru II单羰基络合物[Ru（CO）（dmso）5 ] [PF 6 ] 2可以在相对温和的条件下进行卟啉的钌化，该化合物除CO外还具有不稳定的dmso配体。即使这个发现看似微不足道，但这只是使用Ru II的第二个例子羰基化合物用于卟啉的钌化，第一个已在近50年前被报道，但后来被忽略了。从实际的角度来看，我们展示了丙酸作为溶剂与Ru 3（CO）12（1）一起进行中性和阴离子模型卟啉的钌化的惊人效果。与文献中描述的方法相比，该方法在反应速率和产率（例如TPP在30分钟内在140℃下100％钌化）方面都是极其有效和有利的。
• Ordered Supramolecular Porphyrin Arrays from a Building Block Approach Utilizing Pyridylporphyrins and Peripheral Ruthenium Complexes and Identification of a New Type of Mixed-Metal Building Block
  作者：Enzo Alessio、Michela Macchi、Sarah L. Heath、Luigi G. Marzilli

  DOI：10.1021/ic970340u

  日期：1997.11.1

  Supramolecular ruthenium complexes (Ru-PyPs) with 4-pyridyl/phenyl porphyrins (PyPs) have been designed and characterized spectroscopically. Ruthenium-dimethyl sulfoxide (Me2SO) complexes and their carbonyl derivatives were used as precursors to synthesize adducts with Ru:PyP ratios of 1:1 and 1:2 (monomers), 2:1 (dimers), and 4:1 (tetramers). For example, treatment of mono-(pyridyl)porphyrin MPyP (5-(4-pyridyl)-10,15, 20-triphenylporphyrin) with cis,fac-RuCl2(Me2SO)(3)(CO) yielded the 1:1 monomer cis,cis,cis-RuCl2(Me2SO)(2)(CO)(MPyP), while reaction with trans,cis,cis-RuCl2(Me2SO)(4) or trans,cis,cis-RuCl2(CO)2(Me2SO)2 (2:1 ratio) gave the 1:2 monomers trans,cis,cis-RuCl2(Me2SO)(2)(MPyP)(2) and tmr cis,cis-RuCl2(CO)(2)(MPyP)(2), respectively. Synthesis of the dimers, (cis-DPyP) [cis,cis,cis-RuCl2(Me2SO)2(CO)](2) and (trans-DPyP) [fis, cis, cis-RuCl2(Me2SO)(2)(CO)](2), was accomplished by reaction of the bis-(pyridyl)porphyrins, cis-DPyP (5,10-bis(4-pyridyl)-15,20-diphenylporphyrin) and trans-DPyP (5,1 5-bis(4-pyridyl)-10,20-diphenylporphyrin), respectively, with an excess of cis,fac-RuCl2(Me2SO)3(CO), Similarly, treatment of 5,10,15,20-tetrakis(4-pyridyl)porphyrin (TPyP) with an excess of cis,fac-RuCl2(Me2SO)(3)(CO) yielded the symmetric tetramer, (TPyP)[cis,cis,cis-RuCl2(Me2SO)(2)(CO)(4)](4). H-1 NMR spectroscopy proved particularly useful for characterizing the Ru-PyPs. Coordination of Ru to the Lt-pyridyl groups affected mainly the resonances of the pyridyl ring(s) of the PyPs, causing downfield shifts (H2,6 signals from 0.3 to 0.9 ppm; H3,5 from 0.03 to 0.18 ppm). The pyrrole proton resonances were particularly informative about the geometry of the porphyrin, Treatment of selected Ru-PyP adducts with an excess of zinc acetate produced the corresponding zinc compounds, Ru-Zn . PyPs, in good yield. Most of the Ru-PyPs and Ru-Zn . PyPs are quite soluble in organic solvents like CHCl3 and very robust in solution, where they remain intact for weeks. TH NMR and electronic absorption spectra provided evidence that only the Ru-Zn PyPs with residual Me2SO units self-assemble spontaneously in solution. The observations are consistent with a self-assembly mode process occuring between the oxygen atom of a Me2SO ligand of one molecule and the zinc of another molecule.
• Carbonyl Derivatives of Chloride-Dimethyl Sulfoxide-Ruthenium(II) Complexes: Synthesis, Structural Characterization, and Reactivity of Ru(CO)x(DMSO)4-xCl2 Complexes (x = 1-3)
  作者：E. Alessio、B. Milani、M. Bolle、G. Mestroni、P. Faleschini、F. Todone、S. Geremia、M. Calligaris

  DOI：10.1021/ic00123a004

  日期：1995.9

  The reactivity of cis- and trans-RuCl2(DMSO)(4) with carbon monoxide has been thoroughly investigated. Depending on the choice of the solvent and the reaction conditions, cis-RuCl2(DMSO)(4) reacts with CO at ambient pressure replacing one, two or three DMSO molecules. The following derivatives have been isolated: trans,cis,cis-Ru-(CO)(DMSO)(DMSO)(2)Cl-2 (1), cis,cis,cis-Ru(CO)(2)(DMSO)(DMSO)Cl-2 (2), cis,trans,cis-Ru(CO)(2)(DMSO)(2)Cl-2 (3) and fac-Ru(CO)(3)(DMSO)Cl-2 (4). Compounds 1, 3 and 4 have been structurally characterized. 1 . 0.5H(2)O: monoclinic, P2(1)/c, Z = 8, a = 15.408(1) Angstrom, b = 15.398(2) Angstrom, c = 14.826(1) Angstrom, beta = 107.46(1)degrees. 3: orthorhombic, Pca2(1), Z = 8, a = 15.853(3) Angstrom, b = 11.380(2) Angstrom, c = 14.874(2) Angstrom. 4: orthorhombic, P2(1)2(1)2(1), Z = 4, a = 7.300(2) Angstrom, b = 9.297(2) Angstrom, c = 16.515(4) Angstrom, beta = 107.46(1)degrees. Reaction of trans-RuCl2(DMSO)(4) with CO at room temperature and ambient pressure leads to the replacement of either one or two DMSO ligands, depending on the reaction time, yielding trans,trans,trans-Ru(CO)(DMSO)(DMSO)(2)Cl-2 (5) and cis,cis,trans-Ru(CO)(2)(DMSO)(2)Cl-2 (6). The crystal structure of 5 has been determined. 5: monoclinic, P2(1), Z = 4, a = 7.417(3) Angstrom, b = 26.808(6) Angstrom, c = 8.368(4) Angstrom, beta = 107.55(7)degrees. Complex 3 is the thermodynamically most stable bis(carbonyl) species. Compounds 1-6 represent the first example of well-characterized Ru(II) chloride-DMSO-carbonyl complexes. Their most striking common feature is that coordination of carbon monoxide induces the selective isomerization of the DMSO trans to it from S- to O-bonding. Compounds 1-6 are versatile precursors for the synthesis of carbonylated Ru(II) species in which the DMSO ligands are partially or completely replaced by other ligands. Reaction of 1-6 with pyridine has been investigated and several products were isolated. The reactions were often accompanied by a geometrical isomerization. Complex 1 yields cis,cis,cis-Ru(CO)(py)-(DMSO)(2)Cl-2 (7), whose crystal structure has been determined. 7: triclinic, P $($) over bar$$ 1, Z = 2, a = 7.129(3) Angstrom, b = 7.918(2) Angstrom, c = 14.516(7) Angstrom, alpha = 84.70(3)degrees, beta = 88.14(3)degrees, gamma = 77.87(3)degrees. Complex 3 can replace either one DMSO ligand, forming the two geometrical isomers cis,cis,cis-Ru(CO)(2)(py)(DMSO)Cl-2 (8) and cis,trans,cis-Ru-(CO)(2)(py)(DMSO)Cl-2 (9), or two DMSO ligands, yielding cis,cis,trans-Ru(CO)(2)(py)(2)Cl-2 (10), where a cis to trans isomerization of the two chlorides occurred. Also the crystal structure of 9 has been determined; 9: triclinic, P $($) over bar$$ 1, Z = 4, a = 7.939(3) Angstrom, b = 12.863(5) Angstrom, c = 14.133(3) Angstrom, alpha = 105.95(2)degrees, beta = 95.10(2)degrees, gamma = 99.02(2)degrees. fac-Ru(CO)(3)(py)Cl-2 (11) was obtained from 4, while cis,cis,trans-Ru(CO)(DMSO)(py)(2)Cl-2 (12) and cis,cis,trans-Ru(CO)(2)(py)(2)Cl-2 (10) were synthesized from 5 and 6, respectively.
• Water-Soluble Ruthenium(II) Carbonyls with 1,3,5-Triaza-7-phosphoadamantane
  作者：Federica Battistin、Gabriele Balducci、Barbara Milani、Enzo Alessio

  DOI：10.1021/acs.inorgchem.8b00698

  日期：2018.6.18

  and cis-RuCl2(PTA)4 (15, 16) isomers with CO, afforded only one new Ru(II)-PTA carbonyl, the cationic species cis-[RuCl(CO)(PTA)4]Cl (17). In general, the choice of the solvent was very relevant for obtaining the products with high yield and purity. We were unable to isolate Ru(II)-PTA compounds with more than two carbonyls. The thermodynamically preferred species have CO trans to Cl and two mutually

  通过在配位领域中引入高度水溶性的1,3,5-三氮杂-7-磷金刚烷（PTA）支撑配体，我们制备具有改善的水溶性的新Ru（II）前体的策略的延续，在这项工作中，我们讨论了Ru（II）-PTA羰基化合物的很大程度上未开发的制备方法。使用了两种互补的合成方法：（1）处理一系列通式为RuCl2（CO）n（dmso）4- n的中性Ru（II）-CO-dmso化合物（n = 1-3，1-5 ）与PTA；（2）Ru（II）-PTA配合物与CO的反应。通过第一种方法，我们获得并充分表征了每个Ru原子带有一个至三个PTA配体的七个新型中性化合物，即四个单羰基，顺式，顺式，反式RuCl2（CO）（dmso-S）（PTA）2（6），反式RuCl2（CO）（PTA）3（7），顺式，mer-RuCl2（CO）（PTA）3（8），反式，反式，反式RuCl2（CO）（OH2）（PTA）2（10）和三个二羰基，反式，反式，
• New Cationic and Neutral Ru(II)- and Os(II)-dmso carbonyl Compounds
  作者：Ioannis Bratsos、Simone Calmo、Ennio Zangrando、Gabriele Balducci、Enzo Alessio

  DOI：10.1021/ic401940z

  日期：2013.10.21

  The preparation and structural characterization of three cationic Ru(II)-dmso carbonyls and of four neutral mono- and dicarbonyl Os(II)-dmso derivatives is reported. The two monocarbonyl species fac-[Ru(CO)(dmso-O)3(dmso-S)2][PF6]2 (11) and cis,cis,cis-[RuCl(CO)(dmso-O)2(dmso-S)2][PF6] (12) were obtained from the neutral monocarbonyl precursor cis,trans,cis-[RuCl2(CO)(dmso-O)(dmso-S)2] (3) upon stepwise

  报道了三种阳离子Ru（II）-dmso羰基化合物以及四种中性单-和二羰基Os（II）-dmso衍生物的制备和结构表征。两个单羰基物质fac- [Ru（CO）（dmso-O）3（dmso-S）2 ] [PF 6 ] 2（11）和cis，cis，cis- [RuCl（CO）（dmso-O）2（dmso-S）2 ] [PF 6 ]（12）是从中性单羰基前体顺式，反式，顺式-[RuCl 2（CO）（dmso-O）（dmso-S）2制备的。]（3）用dmso逐步替换氯化物时，dmso分别通过氧原子结合。在中性三羰基前体fac- [RuCl ]处理后，获得了二羰基阳离子络合物顺式，顺式，反式-[Ru（CO）2（dmso-O）2（dmso-S）Cl] [PF 6 ]（PF 6）（13）。在存在DMSO的情况下用AgPF 6取代2（CO）3（dmso-O）]（8）：用dmso-O取代Cl –也暗示另一种d