OsHCl(η2-H2)(CO)(P(C3H7)3)2 | 117526-09-7

• 英文名称: OsHCl(η2-H2)(CO)(P(C3H7)3)2
• 英文别名: OsHCl(η2-H2)(CO)(P-i-Pr3)2；OsHCl(CO)(η2-H2)(P(CH(CH3)2)3)2
• CAS: 117526-09-7
• 化学式: C₁₉H₄₅ClOOsP₂
• 分子量: 577.166
• InChiKey: CNBNWXLSCNAMBG-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：
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• 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：

  OsHCl(η2-H2)(CO)(P(C3H7)3)2 以 not given 为溶剂， 生成 bis(triisopropylphosphane)chloro(hydrido)carbonylosmium(II)(PiPr3)2
  参考文献：
  名称：

  Esteruelas, Miguel A.; Sola, Eduardo; Oro, Luis A., Angewandte Chemie, 1988, vol. 100, # 11, p. 1621 - 1622

  摘要：

  DOI：
• 作为产物：
  描述：

  bis(triisopropylphosphane)chloro(hydrido)carbonylosmium(II)(PiPr3)2 在 氢气 作用下， 以 苯 为溶剂， 生成 OsHCl(η2-H2)(CO)(P(C3H7)3)2
  参考文献：
  名称：

  Esteruelas, Miguel A.; Sola, Eduardo; Oro, Luis A., Angewandte Chemie, 1988, vol. 100, # 11, p. 1621 - 1622

  摘要：

  DOI：

文献信息

• OsHCl(CO)(PiPr3)2 as catalyst for ring-opening metathesis polymerization (ROMP) and tandem ROMP–hydrogenation of norbornene and 2,5-norbornadiene
  作者：N Cobo

  DOI：10.1016/j.jcat.2004.01.028

  日期：2004.4.25

  Complex OsHCl(CO)(PiPr3)2 catalyzes the ring-opening metathesis polymerization (ROMP) of norbornene and 2,5-norbornadiene to give poly(norbornene) and poly(norbornadiene), respectively. In both cases the resulting polymers have a high cis (74–95%) content. The stereoregularity or tacticity of the cyclopentane and cyclopentene ring sequences in poly(norbornene) and poly(norbornadiene) estimated from

  配合物OsHCl（CO）（P i Pr 3）2催化降冰片烯和2,5-降冰片二烯的开环复分解聚合（ROMP），分别得到聚降冰片烯和聚降冰片二烯。在这两种情况下，所得的聚合物均具有较高的顺式（74–95％）含量。发现由氢化衍生物的13 C 1 H} NMR谱估计的聚（降冰片烯）和聚（降冰片二烯）中的环戊烷和环戊烯环序列的立构规整度或立构规整度是间同立构的。复合OsHCl（CO）（P i Pr 3）2在降冰片烯和2,5-降冰片二烯的串联ROMP加氢中也很活跃。在40°C和3 atm的H 2下，聚降冰片烯在48小时内被完全氢化，而聚降冰片二烯在75°C和3 atm的H 2下在48小时内被完全氢化。RuHCl（CO）（P i Pr 3）2络合物在降冰片烯的ROMP和串联ROMP加氢中也具有活性，分别获得反式聚降冰片烯和氢化聚降冰片烯。
• Kinetic and mechanistic investigation of the sequential hydrogenation of phenylacetylene catalyzed by OsHCl(CO)(PR3)2 [PR3 = PMe-tert-Bu2 and P-i-Pr3]
  作者：Antida Andriollo、Miguel A. Esteruelas、Uwe Meyer、Luis A. Oro、Roberto A. Sanchez-Delgado、Eduardo Sola、Cristina Valero、Helmut Werner

  DOI：10.1021/ja00201a024

  日期：1989.9
• 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.
• Ligand exchange processes of OsHCl(CO)(L)(PR3)2 (L=vacant, H2, R′CN, O2; R=Cy, i-Pr)
  作者：J.Scott Parent、Neil T. McManus、Garry L. Rempel、William P. Power、Todd B. Marder

  DOI：10.1016/s1381-1169(98)00005-3

  日期：1998.10

  The reactivity of complexes formed by the addition of O-2, H-2 and R'CN to OsHCl(CO)(PR3)(2) (1a:R = Cy; 1b:R = i-Pr) has been examined. Under 24 bar H-2 and 65 degrees C, the dioxygen ligand of OsHCl(CO)(O-2)(PR3)(2) (2a,b) is displaced to yield the trans-hydridodihydrogen complexes OsHCl(eta(2)-H-2)(CO)(PR3)(2) (3a,b). Measurements of the equilibrium constant, K-H2 = [3a]/[1a][H-2], for the direct addition of H-2 to 1a yield Delta H degrees = -49.1 +/- 2.4 kJ/mol and Delta S degrees = -95.7 +/- 7.9 J/mol K. 1a,b react reversibly with aryl and alkyl nitriles to produce the isolable complexes, OsHCl(CO)(R'CN)(PR3)(2) (4a,b). The phosphine ligands of la,b and 3a,b exchange with unbound, bulky alkyl phosphines at a rate that is slow relative to the NMR timescale. In the presence of excess PCy3, complex 3b yields the exchange products OsHCl(eta(2)-H-2)(CO)(Pi-Pr-3)(PCy3) and 3a. While a tris-phosphine complex cannot be detected, limited kinetic data characterize the exchange as associative process. (C) 1998 Elsevier Science B.V. All rights reserved.