Os3(CO)10(μ-SCH2Me2CH2) | 129570-97-4

• 英文名称: Os3(CO)10(μ-SCH2Me2CH2)
• CAS: 129570-97-4
• 化学式: C₁₅H₁₀O₁₀Os₃S
• 分子量: 952.904
• InChiKey: RHXLTXHVISINLT-UHFFFAOYSA-N

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：

  Os3(CO)10(μ-SCH2Me2CH2) 以 正己烷 为溶剂， 以47%的产率得到Os3(CO)10{μ-SCH2C(CH3)2CH2}
  参考文献：
  名称：

  Evidence for the activation of thietanes to ring opening by nucleophiles through bridging coordination

  摘要：

  The reaction of Os3(CO)10(mu-SCH2CME2CH2) (1) with [Et4N]+Cl- in CH2Cl2 yielded after acidification the complex Os3(CO)10[mu-SCH2CMe2CH2Cl](mu-H) (3; 55%), which contains a chloroneopentanethiolato ligand that is believed to have been formed by the nucleophilic ring opening of the thietane ligand in 1. In contrast, the reaction of the ring-opened complex Os3(CO)10[mu-SCH2CMe2CH2] (4) with [Et4N]+Cl- yielded only the cluster-opened product [Et4N]+[Os3(CO)9(mu-SCH2CMe2CH2)-(mu-Cl)]- (5; 87%). Compounds 3 and 5 were characterized crystallographically.

  DOI：

  10.1021/om00054a006
• 作为产物：
  描述：

  3,3-Dimethyl-thietan 、 bis(acetonitrile)decacarbonyltriosmium 以 二氯甲烷 为溶剂， 以41%的产率得到Os3(CO)10(μ-SCH2Me2CH2)
  参考文献：
  名称：

  Ring-opening oligomerization of 3,3-dimethylthietane by a triosmium cluster complex

  摘要：

  The complexes Os3(CO)11(SCH2CMe2CH2) (1) and Os3(CO)10(mu-SCH2CMe2CH2) (2) were synthesized by the reactions of 3,3-dimethylthietane (3,3-DMT) with Os3(CO)11(NCMe) and Os3(CO)10(NCMe)2, respectively. Complex 2 was characterized crystallographically and was found to contain an S-coordinated bridging DMT ligand. Compound 2 reacts with 3,3-DMT at 25-degrees-C to yield the complex Os3(CO)10[mu-SCH2CMe2CH2)3] (3), which contains an 11-osmio-2,2,6,6,10,10-hexamethyl-4,7-dithiaundecanethiolato ligand formed by the ring-opening oligomerization of three 3,3-DMT molecules. Complex 3 was characterized crystallographically and was found to contain a bridging thiolato group and sigma-bonded carbon at the termini of the oligomer and one thioether group coordinated to an open cluster. Compound 1 does not oligomerize 3,3-DMT at 25-degrees-C. When heated to 125-degrees-C, 3 eliminated carbon monoxide and was transformed to two isomers Os3(CO)9[mu-SCH2CMe2CH2)3] 4 and 5 that contain closed triosmium clusters. Both also contain the same oligomeric grouping of the three 3,3-DMT ligands as in 3, but differ in the coordination position of the thiolato bridge. When heated to 120-degrees-C under 650 psi CO, compounds 3 and 5 were converted to Os3(CO)10[mu-O = C(CH2CMe2CH2S)3] (6), 68% by carbonylation. The C-terminus of the oligomer is functionalized by a CO group that bridges an open edge of the cluster in a mu-eta-2-O = C bridging mode. Both thioether groups are uncoordinated in 6. Compound 6 is decarbonylated at 68-degrees-C under nitrogen to yield Os3(CO)9[mu-O = C(CH2CMe2CH2S)3] (7), 46%. Compound 7 is similar to 6 except that one of the thioether groups of the oligomer is coordinated. Crystallographic data. For 2: space group P2(1)/c, a = 14.075 (3) angstrom, b = 22.143 (4) angstrom, c = 14.788 (3) angstrom, beta = 108.37 (2)o, Z = 2, 3227 reflections, R = 0.046. For 3: space group P1BAR, a = 12.025 (3) angstrom, b = 16.596 (4) angstrom, c = 9.738 (2) angstrom, alpha = 95.84 (2)o, beta = 108 76 (2)o, gamma = 79.96 (2)o, Z = 2, 2867 reflections, R = 0.029. For 4: space group P1BAR, a = 11.102 (2) angstrom, b = 14.724 (3) angstrom, c = 10.767 (2) angstrom, alpha = 104.94 (2)o, beta = 99.19 (1)o, gamma = 72.73 (1)o, Z = 2, 3519 reflections, R = 0.023. For 5: space group P2(1)/n, a = 15.153 (3) angstrom, b = 24.453 (7) angstrom, c = 10.359 (2) angstrom, beta = 90.58 (2)o, Z = 4, 2801 reflections, R = 0.031. For 6: space group P1BAR, a = 9.909 (2) angstrom, b = 20.642 (4) angstrom, c = 9.283 (2) angstrom, alpha = 101.30 (2)o, beta = 103.30 (2)o, gamma = 96.92 (2)o, Z = 2, 2568 reflections, R = 0.048. For 7: space group P2(1)/c, a = 12.256 (3) angstrom, b = 12.054 (2) angstrom, c = 23.110 (3) angstrom, beta = 103.53 (1)o, Z = 4, 3049 reflections, R = 0.033.

  DOI：

  10.1021/ja00005a027

文献信息

• Adams, Richard D.; Pompeo, Michael P., Organometallics, 1992, vol. 11, # 4, p. 1460 - 1465
  作者：Adams, Richard D.、Pompeo, Michael P.

  DOI：——

  日期：——
• Transformations of strained-ring thioethers by metal cluster complexes. Nature of the ring opening of a bridging 3,3-dimethylthietane ligand in a triosmium cluster complex
  作者：Richard D. Adams、Michael P. Pompeo

  DOI：10.1021/om00160a009

  日期：1990.10
• Transformations of 3,3-dimethylthietane in triosmium cluster complexes
  作者：Richard D. Adams、Judy A. Belinski、Michael P. Pompeo

  DOI：10.1021/om00042a015

  日期：1992.6

  Three products were isolated from the thermolysis of either Os3(CO)11[SCH2CMe2CH2] (1) or Os3-(CO)10[mu-SCH2CMe2CH2] (2) at 97-degrees-C. These were identified on the basis of IR and H-1 NMR spectroscopy and single-crystal X-ray diffraction analyses as Os2(CO)6[mu-SCH2C(Me)CH2(CH2)](mu-H) (3; 14%,18%), Os3(CO)9[mu-SCH2C(Me)2CH](mu-H) (4; 18%, 21%) and Os4(CO)12(mu-CO)[mu-SCH2CMe2CH2] (5; 8%, 12%). Treatment of 4 with H2/CO (1200 psi, 5/1) at 97-degrees-C yielded 3 (47%) and Os3(CO)10[mu-SCH2CMe3](mu-H) (23%). When subjected to UV irradiation, 1 and 2 were converted to the metallacyclic isomer Os3( CO)10[mu-SCH2CMe2CH2] (6) in 30% and 47% yields, respectively. Thermolysis of 6 at 97-degrees-C produced 3 and 4. Compound 6 was carbonylated (500 psi) at 70-degrees-C to yield Os3(CO)11[mu-SCH2C(Me)2CH2] (7; 11%) and Os3(CO)11[mu-SCH2C(Me)2CH2C=O] (8; 42%), which is formed by a CO insertion into the metal-carbon bond of the metallacycle. Compound 6 reacts with [(Et)4N]+Cl- at 25-degrees-C to form [Os3(CO)9(mu-SCH2C-(Me)2CH2) (mu-Cl)]-[(Et)4N]+ (9; 87%) by decarbonylation and addition of Cl- to the cluster. Complexes 7-9 were also characterized by single-crystal X-ray diffraction analyses. All three compounds contain open clusters of the three metal atoms in which the sulfur atom bridges the pair of metal atoms that are not mutually bonded. Compound 8 contains a thiametallacyclohexanone ring formed by the insertion of a CO group into the metal-carbon bond of the metallacycle in 7. Compound 9 was formed by the cluster-opening addition of chloride to 6 and contains a bridging chloro ligand. Data for 3: space group = P2(1)/m, a = 6.3804 (8) angstrom, b = 14.149 (2) angstrom, c = 8.649 (1) angstrom, beta = 96.70 (1)-degrees, Z = 2, 1019 reflections, R = 0.036. Data for 4: space group = P1BAR, a = 9.330 (2) angstrom, b = 14.352 (2) angstrom, c = 8.656 (2) angstrom, alpha = 93.73 (2)-degrees, beta = 117.58 (1)-degrees, gamma = 101.09 (2)-degrees, Z = 2, 1977 reflections, R = 0.023. Data for 7: space group = Pn, a = 9.791 (2) angstrom, b = 10.5812 (9) angstrom, c = 10.957 (1) angstrom, beta = 102.09 (1)-degrees, Z = 2,1693 reflections, R = 0.038. Data for 8: space group P1BAR, a = 14.108 (4) angstrom, b = 16.628 (7) angstrom, c = 9.985 (4) angstrom, alpha = 90.09 (4)-degrees, beta = 93.24 (3)-degrees, gamma = 81.97 (3)-degrees, Z = 4,3838 reflections, R = 0.048. Data for 9: space group = P2(1)/n, a = 9.320 (2) angstrom, b = 18.484 (5) angstrom, c = 17.943 (3) angstrom, beta = 95.04 (2)-degrees, Z = 4, 2886 reflections, R = 0.024.