| 102513-22-4

• CAS: 102513-22-4
• 化学式: C₂₀H₄₃ClO₂OsP₂
• 分子量: 603.161
• InChiKey: NBJJHIMDMJCWDY-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：

  在 HCl 作用下， 以 苯 为溶剂， 以88%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

文献信息

• Five- and six-coordinate hydrido(carbonyl)-ruthenium(II) and -osmium(II) complexes containing triisopropylphosphine as ligand
  作者：M.A. Esteruelas、H. Werner

  DOI：10.1016/0022-328x(86)80134-6

  日期：1986.4

  five-coordinate hydrido(carbonyl) complexes MHCl(CO)(PPri3)2 (I, M = Ru; II, M = Os) have been prepared in excellent yields from MCl3 · aq and PPri3 in methanol. They react with ligands L such as P(OMe)3, PMe3, CO, and olefins CH2CHR (R = H, CO2Me, CN, COMe) to produce the six-coordinate compounds MHCl(CO)(PPri3)2L (III–VI, VIII–XIII). Displacement of the chloride ligand in I,II by acetate or acetylacetonate

  由甲醇中的MCl 3 ·aq和PPr i 3以极高的收率制备了五配位的氢化羰基配合物MHCl（CO）（PPr i 3）2（I，M = Ru; II，M = Os）。它们与配位体L，例如P（OME）反应3，PME 3，CO，和烯烃CH 2 CHR（R = H，CO 2 Me中，CN，来），以产生所述六配位化合物MHCl（CO）（PPR i 3）2 L（III–VI，VIII–XIII）。通过乙酸在I，II氯化物配体的位移或乙酰丙酮也通向六配位配合物MH（η 2 -O 2 CME）（CO）（PPR我3）2（XVI，XVII）和MH（η 2 -acac）（CO）（PPR我3）2（XVIII，XIX）表示。还描述了二氯配合物反式-OsCl 2 [P（OPH）3 ] 4（XXI）和反式-RuCl 2（PMe 3）3 P（OPh）3（XXII）的合成。