OsH3(η(5)-C5H5)(PiPr3) | 252573-10-7

• 英文名称: OsH3(η(5)-C5H5)(PiPr3)
• CAS: 252573-10-7
• 化学式: C₁₄H₂₉OsP
• 分子量: 418.558
• InChiKey: FRTLJVIZXYUJIA-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

• 作为反应物：
  描述：

  tetrafluoroboric acid diethyletherate 、 OsH3(η(5)-C5H5)(PiPr3) 以 乙醚 为溶剂， 以93%的产率得到[OsH2(η5-C5H5)(η2-H2)(P(i)Pr3)]BF4
  参考文献：
  名称：

  Reduction and C(sp²)−H Bond Activation of Ketones Promoted by a Cyclopentadienyl-Osmium- Dihydride-Dihydrogen Complex

  摘要：

  The dihydride-dihydrogen complex [OsH2(eta(5)-C5H5)(eta(2)-H-2)((PPr3)-Pr-i)]BF4 (2) has been prepared by addition of HBF4 center dot OET2 to OsH3(eta 5-C5H5)((PPr3)-Pr-i) (1), and its reactions with benzylideneacetone, methyl vinyl ketone, acetophenone, and benzylideneacetophenone have been studied. The reaction with benzylideneacetone leads initially to [OsH2(eta 5-C5H5){k(1)-OC(CH3)CH=CHPh}-((PPr3)-Pr-i)]BF4 (3), which in dichloromethane is converted to the hydroxyallyl derivative [OsH-(eta 5-C5H5){eta(3)-CH2C(OH)CHCH2Ph}((PPr3)-Pr-i)]BF4 (4). Complex 4 releases 4-phenylbutan-2-one, and the resulting metallic fragment activates a C-beta(sp(2))-H bond of a new molecule of benzylideneacetone to give [OsH(eta 5-C5H5){C(Ph)CHC(O)CH3}((PPr3)-Pr-i)]BF4 (5), which affords Os(eta 5-C5H5){C(Ph)CHC(O)CH3}(PiPr(3)) (6) by deprotonation with NaOCH3. The reaction of 2 with methyl vinyl ketone gives ethyl methyl ketone and [OsH(eta(5)-C5H5){CHCHC(O)-CH3}((PPr3)-Pr-i)]BF4 (9). The latter can also be obtained from Os(eta(5)-C5H5)Cl{eta(2)-CH2=CHCH(O)-CH3}((PPr3)-Pr-i) (7) via the intermediate [Os(eta(5)-C5H5){CH2CHC(O)CH3}((PPr3)-Pr-i)]BF4 (8). Treatment of 9 with NaOCH3 leads to an equilibrium mixture of Os(eta(5)-C5H5){CHCHC(O)CH3}-((PPr3)-Pr-i) (10) and the hydride-vinylidene OsH(eta(5)-C5H5){=C=CHC(O)CH3}((PPr3)-Pr-i) (11). The reaction of 2 with acetophenone gives 1-phenylethanol and the orthometalated derivative [OsH(eta(5)-C5H5{C6H4C(O)CH3}((PPr3)-Pr-i)]BF4 (13), which is deprotonated with NaOCH3 to give OsH(eta(5)-C5H5){C6H4C(O)CH3}((PPr3)-Pr-i) (14), whle the reaction of 2 with benzylidene-actophenone leads to [OsH(eta(5)-C5H5){C(Ph)CHC(O)Ph}((PPr3)-Pr-i)]BF4 (15), which yields Os(eta(5)-C5H5){C(Ph)CHC(O)Ph}((PPr3)-Pr-i) (16) by deprotonation. Complexes 3, 10, and 13 have been characterized by X-ray diffraction analysis.

  DOI：

  10.1021/om0508177
• 作为产物：
  描述：

  OsH2(η(5)-C5H5)Cl(PiPr3) 、 sodium tetrahydroborate 以 甲醇 、 甲苯 为溶剂， 以47%的产率得到OsH3(η(5)-C5H5)(PiPr3)
  参考文献：
  名称：

  Oxidative Addition of HX (X = H, SiR₃, GeR₃, SnR₃, Cl) Molecules to the Complex Os(η⁵-C₅H₅)Cl(PⁱPr₃)₂

  摘要：

  The cyclopentadienyl complex Os(eta(5)-C5H5)Cl((PPr3)-Pr-i)(2) (1) reacts with molecular hydrogen to give a mixture of the isomers transoid-dihydride OsH2(eta(5)-C5H5)Cl((PPr3)-Pr-i) (2a) and cisoid-dihydride OsH2(eta(5)-C5H5)Cl((PPr3)-Pr-i) (2b). Isomer 2a has a rigid structure in solution. However, the hydride ligands of 2b undergo a thermally activated site exchange process and show quantum exchange coupling. The reaction of the isomeric mixture of 2a and 2b with NaBH4 and methanol leads to the trihydride OsH3(eta(5)-C5H5)((PPr3)-Pr-i) (3) In solution, the cisoid hydride ligands of this complex also undergo a thermally activated site exchange process. The activation parameters are Delta H double dagger = 15.1 +/- 0.3 kcal . mol(-1) and Delta S double dagger = 0.5 +/- 0.7 cal . mol(-1) . K-1. Complex 1 also reacts with group 14 element hydride compounds to afford OsH(eta(5)-C5H5)Cl(ER3)((PPr3)-Pr-i) [ER3 = SiEt3 (4), Si(CH2-CH=CH2)Me-2 (5), SiPh3 (6), SiHPh2 (7), SiH2-Ph (8), GeEt3 (9), GePh3 (10), GeHPh2 (11), (SnBu3)-Bu-n (12), SnPh3 (13)]. The structure of 7 has been determined by an X-ray investigation. The distribution of ligands around the metallic center can be described as a piano stool geometry with the triisopropylphosphine and diphenylsilyl ligands disposed mutually transoid. Complex 12 reacts with (HSnBu3)-Bu-n to give the dihydride-stannyl derivative OsH2(eta(5)-C5H5)((SnBu3)-Bu-n)((PPr3)-Pr-i) (14) The reaction of 1 with HCl leads to a mixture of the monohydrides OsH(eta(5)-C5H5)Cl-2((PPr3)-Pr-i) (15) and [OsH(eta(5)-C5H5)Cl((PPr3)-Pr-i)(2)](+) (16) Complexes 15 and 16 can also be obtained by reaction of 6 with HCl and by protonation of 1 with HER, respectively.

  DOI：

  10.1021/om990235n