ditert-butyl(methyl)phosphane;dichloro(dihydrido)osmium | 131296-71-4

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: ditert-butyl(methyl)phosphane;dichloro(dihydrido)osmium
• CAS: 131296-71-4
• 化学式: C₁₈H₄₄Cl₂OsP₂
• 分子量: 583.601
• InChiKey: IRWCTXBEARUGJK-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  8.23
• 重原子数：
  23.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  ditert-butyl(methyl)phosphane;dichloro(dihydrido)osmium 在 NaBH₄ 、 CH₃OH 作用下， 以 苯 为溶剂， 以52%的产率得到
  参考文献：
  名称：

  八面体烷基氢os（II）配合物[OsH（R）（CO）2（PR'3）2]的合成，分子结构和反应活性。

  摘要：

  In contrast to the reaction of [OsH(eta-1-BH4)(CO)(PR'3)2] (2a,b) with methanol under reflux, which gives the dihydrides cis,cis,trans-[OsH2(CO)2(PR'3)2] (4a,b), the corresponding reaction with ethanol or 2-methoxyethanol under the same conditions leads to the formation of the alkylhydridoosmium(II) complexes [OsH(R)(CO)2(PR'3)2] (5a,b (R = CH3), 6a,b (R = MeOCH2)) in good yields. The X-ray structural analysis of 5a reveals an octahedral coordination sphere around the osmium center with the CO ligands in cis and the phosphines in trans positions. Reactions of 5a,b with electrophiles preferentially leads to cleavage of the Os-CH3 bond; thus, on treatment with HX (X = Cl, CH3CO2, CF3CO2) the monohydrides [OsHX(CO)2(PR'3)2] (11, 12, 13a,b) are formed. Protonation of 5a with HBF4 in ether/acetone yields quantitatively the cationic hydrido complex [OsH(acetone)(CO)2(PiPr3)2]BF4 (15) whereas from 5a,b and HBF4 in the presence of water the compounds [OsH(H2O)(CO)2(PR'3)2]BF4 (16a,b) are obtained. Complex 15 reacts with acetonitrile, trimethyl phosphite, or pyrazole by displacement of the acetone ligand to give the compounds [OsH(L)(CO)2(PiPr3)2]BF4 (17-19). Subsequent reaction of 19 (L = pyrazole) with the dimers [M(mu-OMe) (diolefin) ] 2 (20, 22, M = Rh; 2 1, M = Ir) produces the heterobinuclear complexes 23-25; in these the metal centers (Os and Rh or Ir) are bridged by a hydride and a pyrazolyl group. Treatment of 15 with methyl vinyl ketone and CO2Me-substituted alkynes RC=CO2Me gives cationic four- and five-membered metallacycles 26-29 which are formed by a Markovnikov or an anti-Markovnikov type of insertion of the unsaturated substrate into the Os-H bond.

  DOI：

  10.1021/om00042a018
• 作为产物：
  描述：

  二叔丁基甲基膦 、 氯化锇三水合物 以 异丙醇 为溶剂， 以80%的产率得到ditert-butyl(methyl)phosphane;dichloro(dihydrido)osmium
  参考文献：
  名称：

  Aracama; Esteruelas; Lahoz, Inorganic Chemistry, 1991, vol. 30, # 2, p. 288 - 293

  摘要：

  DOI：

文献信息

• Isomeric Hydrido/Vinylidene, MH(halide)(CCH₂)L₂, and Ethylidyne, M(halide)(C−CH₃)L₂ (M = Os, Ru; L = Phosphine), Are Energetically Similar but Not Interconverting
  作者：Montserrat Oliván、Eric Clot、Odile Eisenstein、Kenneth G. Caulton

  DOI：10.1021/om9709493

  日期：1998.3.1

  It is shown that there is no deuterium-isotope incorporation in the vinylidene CHPh group of RuDX(CCHPh)((PBu2Me)-Bu-t)(2) (X = Cl, I) on the time scale of 24 h at 25 degrees C, which indicates that the (unobserved) isomeric alkylidyne species RuX(CCHDPh)((PBu2Me)-Bu-t)(2) is not readily accessible under these conditions. Ab initio (B3LYP) calculations on the model MHCl(CCH2)(PH3)(2) (M = OS, Ru) show the ethylidyne isomer MCl(CCH3)(PH3)(2) to be close in energy (2.5, -1.1 kcal mol(-1) for Os and Ru, respectively) and effectively inaccessible at 25 degrees C due to the high energy (54.2, 45.5 kcal mol(-1) for Os and Ru, respectively) of the transition state for such a 1,3-migration. In contrast, simple rotation of the CCH2 group of MHCl(CCH2)(PH3)(2) by 180 degrees around the C-C axis is calculated to have a low barrier (8.1, 4.3 kcal mol(-1) for Os and Ru, respectively), indicating this to be the mechanism for isomerization observed in OsHCl(CCHPh)((PPr3)-Pr-i)(2).