| 148629-24-7

• CAS: 148629-24-7
• 化学式: C₁₈H₄₇ClOsP₂
• 分子量: 551.172
• InChiKey: ZOJXCDHBKPQIPB-UHFFFAOYSA-M

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：

  bis(triisopropylphosphane)(dihydrido)dichloroosmium(IV) 、 氢气 以 not given 为溶剂， 生成
  参考文献：
  名称：

  Dihydrogen addition to (PiPr3) 2OsX H4−

  摘要：

  Reaction of H-2 with L2Os(X)(Y)(H)(2) (L=(PPr3)-Pr-i; X, Y = Cl, Br, I) slowly (minutes) gives a 1:1 'adduct'. The X-ray structure of L2OsH4Br2 shows, like the chloride analog, a substantial change in geometry upon reaction with H-2, to give a heavy atom OsX2L2 skeleton of C-2v geometry, with cis halides and trans phosphines. Attempts are made to distinguish between Os(H)(4), Os(H-2)(2) and Os(H)(2)(H-2) structures using J(HD) and T-1min criteria. Study of L2OsXnH4-n species shows no monotonic trend in the Delta G(double dagger) for H-2 loss, being higher for both n=0 and n=2 than for n=1. Studied as a function of X(=Cl, Br, I), H-2 binding to L2Os(H)(2)X-2 is favored enthalpically but disfavored entropically for the larger, least electronegative halide. The X-ray structure of L2OsDCl3 shows this unsaturated species to have significant angular distortions from octahedral geometry, consistent with its diamagnetic character. (C) 1997 Elsevier Science S.A.

  DOI：

  10.1016/s0022-328x(96)06914-8

文献信息

• Quantum Exchange Coupling:  A Hypersensitive Indicator of Weak Interactions
  作者：Roger Kuhlman、Eric Clot、Claude Leforestier、William E. Streib、Odile Eisenstein、Kenneth G. Caulton

  DOI：10.1021/ja970603j

  日期：1997.10.1

  Os(H)(3)ClL2 (L = (PPr3)-Pr-i) forms a 1:1 adduct with L' = PEt3, NH3, MeCN, acetone, methanol, and THF. The case L' = PEt3 permits the dearest identification of adduct structure as pentagonal bipyramidal. For NH3 and MeCN, the respective kinetics of L' loss are measured as Delta H-double dagger = 20.7(3) and 17.6(3) kcal/mol and Delta S-double dagger = 16(1) and 14.7(9) cal/(mol K). For acetone, methanol, and THF, the following respective Delta H degrees and Delta S degrees values for L' binding are measured: Delta H degrees = -10.4(1), -6.66(8), and -5.8(2) kcal/mol; Delta S degrees = -41.8(5), -25.5(3), and -33(1) cal/(mol K). Decoalesced H-1 NMR spectra are reported for several of these Os(H)(3)ClL2L' species, and they show a variety of examples of quantum exchange coupling among the hydride ligands. The values of J(e)x are higher when L' is a more weakly-binding ligand. The quantum exchange coupling constants of Os(H)(3)XL2 (X = Cl, Br, I, OCH2CF3, OCH(CF3)(2)) in CD2Cl2, in toluene, and in methylcyclohexane show an unprecedented decrease of J with increasing temperature, which is attributed to weak formation of Os(H)(3)Cl(solvent)L-2 adducts at low temperature. For L' = CO, adduct formation leads to liberation of coordinated H-2. Excess L' = MeCN or NH3 slowly leads to formation of [Os(H)(3)L'L-2(2)]Cl; the X-ray structure for L' = NH3 is reported. Crystal data (-171 degrees C): a = 11.561(4) Angstrom, b = 14.215(5) Angstrom, c = 8.851(3) Angstrom, alpha = 97.51(2)degrees, beta = 107.73(2)degrees, gamma = 104.47(2)degrees, with Z = 2 in space group . The potential energy was calculated for exchange of 2H of OsH3X(PH3)(2)L (X = Cl with L = no ligand and PH3, X = I with L = no ligand) using effective core potential ab initio methods at the MP2 level. The site exchange is found to be energetically easier for Cl than for I, in agreement with experiment. The hydride site exchange in the seven-coordinate species OsH3Cl(PH3)(3) (a model for coordination of either ligand or solvent to Os) is found to be easier than that in the 16-electron species. No dihydrogen ligand is located on the reaction path for site exchange. The current theory which relates quantum exchange to a tunneling effect was used for calculating J(ex) as a function of temperature. The dynamic study was done using several sets of coordinates, in particular the rotation angle phi and the internuclear distance r between the exchanging H. The vibrational levels have been calculated and the symmetry of each level assigned within the permutation group in order to determine the nature of the nuclear spin function associated with each level. It is found that the rotation, phi, gives rise to the largest tunneling effect but that r cannot be neglected. The influence of the temperature, J(ex)(T), was included by a Boltzmann distribution. The results are in qualitative agreement with experiment in that quantum exchange coupling is larger in the case of Cl than in the case of I. Additional ligand L increases the value of the quantum exchange coupling mostly by lowering the activation energy for pairwise exchange.
• NO binds to unsaturated Os(IV) polyhydrides as a redox reagent
  作者：Joo-Ho Lee、Andrei N. Vedernikov、David Dye、Kenneth G. Caulton

  DOI：10.1016/j.jorganchem.2007.01.059

  日期：2007.7

  Reaction of Os(H)(3)ClL2(L=(PPr3)-Pr-i) with equimolar NO occurs via a detectable paramagnetic species, to form OsCl(NO)L-2 + H-2, then Os(H)(2)Cl(NO)L-2, together with the product of halogen transfer, OsHCl2(NO)L-2. For comparison, equimolar NO and the dichloride Os(H)(2)Cl2L2 react to give OsHCl2(NO)L-2. DFT(PBE) calculations on potential radical intermediates reveal cases where spin density is on NO (vs. on Os), and show how coordinated H-2 can lead to the observed halogen transfer. (c) 2007 Elsevier B.V. All rights reserved.