cis,cis,trans-{OsH2(CO)2(P(iPr)3)2} | 104911-56-0

• 英文名称: cis,cis,trans-{OsH2(CO)2(P(iPr)3)2}
• 英文别名: cis,cis,trans-OsH2(CO)2(P(i)Pr3)2
• CAS: 104911-56-0
• 化学式: C₂₀H₄₄O₂OsP₂
• 分子量: 568.716
• InChiKey: AVEDLFFGTMRFPI-UHFFFAOYSA-N

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：

  OsH(η(2)-H2BH2)(CO)(P(i)Pr3)2 以 甲醇 为溶剂， 以74%的产率得到cis,cis,trans-{OsH2(CO)2(P(iPr)3)2}
  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

• Reactions of a Hexahydride-Osmium Complex with Aldehydes:  Double C−H_α Activation−Decarbonylation and Single C−H_α Activation−Hydroxylation Tandem Processes and Catalytic Tishchenko Reactions
  作者：Pilar Barrio、Miguel A. Esteruelas、Enrique Oñate

  DOI：10.1021/om034389l

  日期：2004.3.1

  the reactions with benzaldehyde, cyclohexanecarboxaldehyde, and isobutyraldehyde lead to products resulting from two C−Hα activation−decarbonylation tandem processes. The reaction with benzaldehyde gives the hydride-phenyl-cis-dicarbonyl derivative OsHPh(CO)2(PiPr3)2 (2) and benzene, while cyclohexanecarboxaldehyde and isobutyraldehyde yield the cis-dihydride-cis-dicarbonyl compound OsH2(CO)2(PiPr3)2

  的六氢化物络合物OSH 6（P我镨3）2（1）激活C-H α醛键。在回流状态下的甲苯中，与苯甲醛，环己烷甲醛和异丁醛的反应导致由两个CHαα活化-脱羰基串联过程产生的产物。与苯甲醛反应生成氢化物-苯基-顺式-二羰基衍生物OSHPh（CO）2（P i Pr 3）2（2）和苯，而环己烷甲醛和异丁醛生成顺式-二氢化物-顺式-二羰基化合物OSH 2（CO）2（P i Pr 3）2（3）和相应的烷烃。在水的存在下1与苯甲醛反应生成2。然而，环己烷甲醛和异丁醛得到羧酸络合物OSH 3（κ 2 -O 2 CR）（P我镨3）2（R =成分Cy（4），（CH 3）2 CH（5）），其也能够得到通过1的反应和相应的羧酸。类似地，治疗1与苯甲酸给出OSH 3（κ 2 -O 2 CPH）（P我镨3）2（6）。固态的5的结构已通过X射线衍射分析确定。around原子周围的配位几何结构可以描述为扭曲的五角双锥体，其中
• Werner, Helmut; Esteruelas, Miguel A.; Meyer, Uwe, Chemische Berichte, 1987, vol. 120, p. 11 - 16
  作者：Werner, Helmut、Esteruelas, Miguel A.、Meyer, Uwe、Wrackmeyer, Bernd

  DOI：——

  日期：——