[OsH2(η5-C5H5)(η2-H2)(P(i)Pr3)]BF4 | 871576-54-4

• 英文名称: [OsH2(η5-C5H5)(η2-H2)(P(i)Pr3)]BF4
• CAS: 871576-54-4
• 化学式: BF₄*C₁₄H₃₀OsP
• 分子量: 506.371
• InChiKey: IHAHXUGKVQUEIW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 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：

  丙酮 、 [OsH2(η5-C5H5)(η2-H2)(P(i)Pr3)]BF4 以 丙酮 为溶剂， 以89%的产率得到OsH2(η5-C5H5)(κ1-OCMe2)(PiPr3)BF4
  参考文献：
  名称：

  One-Pot Dehydrogenative Addition of Isopropyl to Alkynes Promoted by Osmium:  Formation of γ-(η³-Allyl)-α-Alkenylphosphine Derivatives Starting from a Dihydride−Dihydrogen−Triisopropylphosphine Complex

  摘要：

  The dihydride-dihydrogen complex [OsH2(eta(5)-C5H5)(eta(2)-H-2)((PPr3)-Pr-i)]BF4 (1) reacts in acetone with 1-phenyl-1-propyne and 2-butyne to give the gamma-(eta(3)-allyl)-alpha-alkenylphosphine derivatives [OsH(eta(5)-C5H5){kappa(4)-(P,C,C,C)-CH2C[CH2C(CH2)(PPr2)-Pr-i]CHR}]BF4 (R = Ph (2), CH3 (3)), by means of one-pot tandem processes of four reactions. The stable intermediates have been isolated and characterized. In acetone, complex 1 dissociates H-2 and coordinates the solvent to afford [OsH2(eta(5)-C5H5)(kappa(1)-OCMe2)((PPr3)-Pr-i)]BF4 (4), which reacts with a molecule of 1-phenyl-1-propyne or 2-butyne to form [OsH(eta(5)-C5H5)(eta(3)-CH2CHCHR)((PPr3)-Pr-i)]BF4 (R = Ph (5), CH3 (6)), containing the CHR group cisoid disposed to the phosphine and the R substituent anti to C-meso. In dichloromethane, complexes 5 and 6 evolve to the thermodynamic isomers 7 and 8, containing the CHR group cisoid disposed to the hydride and the R substituent syn to C-meso. The reactions of 5 and 6 with a second molecule of the respective alkyne lead to the corresponding Z-olefin and [Os(eta(5)-C5H5){eta(2)-(Z)-CH(CH3)CHR}{kappa(3)-(P,C,C)-[CH2C(CH3)](PPr2)-Pr-i}]BF4 (R = Ph (9), CH3 (10)). The isopropenyl group of the phosphine of 9 and 10 undergoes coupling with a third alkyne molecule to give 2 and 3.

  DOI：

  10.1021/om070004d
• 作为产物：
  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

文献信息

• Preparation and Characterization of a Monocyclopentadienyl Osmium−Allenylcarbene Complex
  作者：Miguel A. Esteruelas、Yohar A. Hernández、Ana M. López、Enrique Oñate

  DOI：10.1021/om700722e

  日期：2007.11.1

  The dihydride-dihydrogen complex [OsH2(eta(5)-C5H5)(eta(2)-H-2)((PPr3)-Pr-i)]BF4 (1) reacts with phenylacetylene to give the allenylcarbene derivative [Os(eta(5)-C5H5)=CPh(eta(2)-CH = C = CHPh)}((PPr3)-Pr-i)]BF4 (2) via the,pi-phenyl acetylene intermediate [Os(eta(5)-C5H5)(eta(2)-PhC CH)((PPr3)-Pr-i)]BF4 (3). The reactions of 2 with NaOMe and LiC CPh afford 3:1 mixtures of two hydride-osmaindene isomers of formula OsH(eta(5)-C5H5)C(C CPh)=CHC6H4}((PPr3)-Pr-i) (4 and 5) instead of the expected osmabenzyne complex.