trihydridotetrakis(triphenylphosphine)osmium(IV) trifluoromethanesulphonate | 105811-85-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: trihydridotetrakis(triphenylphosphine)osmium(IV) trifluoromethanesulphonate
• CAS: 105811-85-6
• 化学式: CF₃O₃S*C₇₂H₆₃OsP₄
• 分子量: 1391.46
• InChiKey: URFORRYZMXHQDV-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  13.02
• 重原子数：
  85.0
• 可旋转键数：
  16.0
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.01
• 拓扑面积：
  57.2
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  、 三苯基膦 在 H₂ 作用下， 以 二氯甲烷-D2 为溶剂， 生成 trihydridotetrakis(triphenylphosphine)osmium(IV) trifluoromethanesulphonate
  参考文献：
  名称：

  Reactions of MH(OTf)(NBD)(PPh₃)₂ (M = Ru, Os) with H₂

  摘要：

  Treatment of RuHCl(NBD)(PPh3)(2) (NBD = norbornadiene) with AgOTf produced RuH(OTf)(NBD)(PPh3)(2). Reaction of RuH(OTf)(NBD)(PPh3)(2) with H-2 in benzene gave norbornene and [(eta (6)-C6H6)RuH(PPh3)(2)]OTf. The same reaction in CD2Cl2 in the presence of added PPh3 produced norbornane and [RuH(PPh3)(4)]OTf. Reaction of OsH3Cl(PPh3)(3) with norbornadiene produced OsHCl(NBD)(PPh3)(2), which was converted to OsH(OTf)(NBD)(PPh3)(2) on treatment with AgOTf. Reaction of OsH(OTf)(NBD)(PPh3)(2) with H-2 in benzene gave norbornane and [(eta (6)-C6H6)OsH(PPh3)(2)]OTf. In dichloromethane, OsH(OTf)(NBD)(PPh3)(2) reacted with H-2 in the presence of added PPh3 to produce norbornane and [OsH3(PPh3)(4)]OTf. Supported by computational studies, it is assumed that; the dihydrogen complexes [MH(H-2)(NBD)(PPh3)(2)](+) (M = Ru, Os) were involved in the hydrogenation reactions. Two reaction pathways for the conversion of [RuH(H-2)(NBD)(PH3)(2)](+) to [RuH(NBE)(PH3)(2)](+) (NBE = norbornene) have been studied by density functional theory calculations. The results show that the first hydrogen transferred to the olefin ligand is more likely from the hydride ligand rather than from the dihydrogen ligand.

  DOI：

  10.1021/om000369x

文献信息

• Complexes of the platinum metals. Part 33. Synthesis of some ruthenium and osmium sulphonate derivatives: X-ray crystal structure of aqua(carbonyl)bis(toluene-p-sulphonato)bis(triphenylphosphine)ruthenium(II)
  作者：P. Alexander Harding、Stephen D. Robinson、Kim Henrick

  DOI：10.1039/dt9880000415

  日期：——

  )(PPh3)2] has been determined by X-ray diffraction methods. The crystals are monoclinic, space group P21/n, with a= 24.382(5), b= 18.075(4), c= 10.729(2)Å, β= 99.03(2)°, and Z= 4. The octahedral ruthenium(II) complex contains monodentate sulphonate ligands (trans to PPh3 and CO) and an aqua ligand (trans to PPh3) with strong hydrogen-bonding interactions between the H atoms of the H2O and the non-co-ordinated

  磺酸RSO 3 H（R = CH 3，CF 3或C 6 H 4 CH 3 - p）与前体[MH 2（CO）（PPh 3）3 ]（M = Ru或OS）和[Ru （CO）3（PPh 3）2 ]或[OSH 2（CO）2（PPh 3）2 ]在苯或甲苯中回流，得到配合物[M（O 3 SR）2（H 2 O）（CO）（ PPh 3）2 ]和[M（O 3 SR）2（CO） 2（PPh 3） 2 ]。前体[期RuH 2（PPH 3） 4 ]和[OSH 4（PPH 3） 3 ]与磺酸在回流的苯，得到η反应6 -苯络合物[MH（η 6 -C 6 H ^ 6）（PPH 3） 2 ] [O 3 SR]。然而，在回流的乙醇中类似的反应产生了[OSH 3（PPh 3） 4 ] [O 3 SCF 3 ]。络合物[Ru（O3 SR） 2（H 2 O）（CO）（PPh 3） 2 ]由可变温度1 H和31 P- 1 H}
• Harding, P. Alexander; Preece, Michael; Robinson, Stephen D., Inorganica Chimica Acta, 1986, vol. 118, p. L31 - L34
  作者：Harding, P. Alexander、Preece, Michael、Robinson, Stephen D.、Henrick, Kim

  DOI：——

  日期：——