OsH6(PPh(i-Pr)2)2 | 91030-50-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: OsH6(PPh(i-Pr)2)2
• 英文别名: [OsH6(diisopropylphenylphosphine)2]
• CAS: 91030-50-1
• 化学式: C₂₄H₄₄OsP₂
• 分子量: 584.761
• InChiKey: DYMAPYDJGQSFIN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.61
• 重原子数：
  27.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  OsH6(PPh(i-Pr)2)2 在 cyclohexa-1,3-diene 作用下， 以 正己烷 为溶剂， 生成 [OsH2(diisopropylphenyl phosphine)2-(μ-H)3-OsH(diisopropylphenylphosphine)2]
  参考文献：
  名称：

  Synthesis and Characterization of the Dinuclear Polyhydrides [Os₂H₇(PPhⁱPr₂)₄]⁺ and [Os₂H₆(PPhⁱPr₂)₄]

  摘要：

  The dinuclear osmium polyhydride [Os2H7((PPhPr2)-Pr-i)(4)][HC(SO2CF3)(2)] (1) was synthesized by the protonation of [OsH6((PPhPr2)-Pr-i)(2)] with bis(trifluoromethylsultonyl)methane. Treatment with amine bases was not able to deprotonate 1, but reaction with potassium hydride gave the corresponding neutral polyhydride [Os2H6((PPhPr2)-Pr-i)(4)] (2). Single crystal X-ray diffraction revealed that 1 and 2 both crystallize in the P2(1)/c space group and are classical polyhydrides containing similar Os(mu-H)(3)Os cores with Os-Os distances of 2.5431(1) angstrom and 2.5448(2) angstrom, respectively. These structures represent rare examples of dinuclear osmium polyhydrides with six or more hydride ligands.

  DOI：

  10.1021/ic900111s
• 作为产物：
  描述：

  bis(diisopropyl(phenyl)-l5-phosphaneyl)dioxoosmium(VIII) chloride 在 LiAlH₄ 作用下， 以 四氢呋喃 为溶剂， 以41%的产率得到OsH6(PPh(i-Pr)2)2
  参考文献：
  名称：

  Connelly, Neil G.; Howard, Judith A.K.; Spencer, John L., Journal of the Chemical Society, Dalton Transactions, 1984, p. 2003 - 2010

  摘要：

  DOI：

文献信息

• An osmium tetrahydroborate complex with unusual dynamic behaviour: X-ray crystal structure of [Os(BH4)H3{P(c-C5H9)3}2](c-C5H9= cyclo-C5H9)
  作者：Peter W. Frost、Judith A. K. Howard、John L. Spencer

  DOI：10.1039/c39840001362

  日期：——

  In the complex [Os(BH4)H3P(c-C5H9)3}2](c-C5H9= cyclo-C5H9), prepared quantitatively from the reaction of [OsH6P(c-C5H9)3}2] with BH3·thf, (thf = tetrahydrofuran), the tetrahydroborate ligand is bound to the metal by two bridging hydrogen atoms which, at 90 °C, exchange rapidly only with the hydride ligands on osmium.

  在配合物[OS（BH 4）H 3 P（CC 5 ħ 9）3 } 2 ]（CC 5 ħ 9 =环-C 5 H ^ 9），从[职业安全与卫生反应定量制备6 P（CC 5 H 9）3 } 2 ]和BH 3 ·thf（thf =四氢呋喃），四氢硼酸酯配体通过两个桥连氢原子与金属结合，在90°C时，氢仅与with上的氢化物配体快速交换。
• Assessment of the "T1 criterion" for distinguishing between classical and nonclassical transition-metal hydrides: hydride relaxation rates in tris(triarylphosphine)osmium tetrahydrides and related polyhydrides
  作者：Peter J. Desrosiers、Lisheng Cai、Zerong Lin、Rosalie Richards、Jack Halpern

  DOI：10.1021/ja00011a019

  日期：1991.5

  [OsH4(PTol3)3] (1, Tol = p-tolyl) and a series of related isotopomers [OsH(x)D4-xP(Tol-o-d2)3}3] (x = 1, 2, 3, and 4) were prepared and hydride spin-lattice relaxation times, T1, determined as a function of temperature for each one. From these measurements the contributions to the relaxation rates of the hydride ligands from the other hydrides and from the ortho protons of the triarylphosphine ligands were determined to be 62% and 33%, respectively. Taking account of these, as well as of the contributions from the phosphorus nuclei (2%) and osmium nucleus (< 0.5%), the calculated relaxation rate, 4.17 s-1 (T1(min) = 238 ms at 500 MHz) agrees to within 3% with the measured one, 4.29 s-1. Similar calculations were performed on 33 other ''classical'' hydrides for which the relaxation rates at 500 MHz ranged from 1.67 to 9.09 s-1 (T1(min) at 500 MHz from 670 to 110 ms). For the majority of these, the calculated and observed relaxation rates agree to within 10%, with contributions from dipole-dipole interactions with nuclei other than metal-coordinated protons accounting for more than 60% of the observed relaxation rates. Such contributions, typically, have been neglected in previous interpretations of T1(min). For ''nonclassical'' hydrides, i.e. those containing eta-2-H-2 ligands, agreement between observed and calculated relaxation rates was less satisfactory. Even in such cases dipole-dipole interactions with nuclei other than metal-coordinated protons account for up to 25% of the observed relaxation rates emphasizing that, in general, such interactions cannot be ignored. There is an overlap between the range of T1(min) values found for classical and nonclassical polyhydrides. For several polyhydrides of undetermined structure, such as [OsH5(PTol3)3]+, [RuH4(PCy3)3], and [RuH6(PCy3)2] (including some that had previously been assigned nonclassical structures on the basis of the ''T1 criterion''), T1(min) is shown to be consistent with both classical and nonclassical structures.