OsH2(η5-C5H5)(κ1-OCMe2)(PiPr3)BF4 | 937169-83-0

• 英文名称: OsH2(η5-C5H5)(κ1-OCMe2)(PiPr3)BF4
• CAS: 937169-83-0
• 化学式: BF₄*C₁₇H₃₄OOsP
• 分子量: 562.435
• InChiKey: BAWNGQIEKDQVIK-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：
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• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  2-丁炔 、 OsH2(η5-C5H5)(κ1-OCMe2)(PiPr3)BF4 以 二氯甲烷 为溶剂， 以77%的产率得到[OsH(η5-C5H5)(η3-CH2CHCHCH3)((i)Pr3)]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：

  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

文献信息

• Reactions of a Dihydride−Osmium(IV) Complex with Aldehydes: Influence of the Substituent at the Carbonyl Group
  作者：Miguel A. Esteruelas、Yohar A. Hernández、Ana M. López、Montserrat Oliván、Lucía Rubio

  DOI：10.1021/om701075d

  日期：2008.2.1

  (1) toward cinnamaldehyde, isovaleraldehyde, and benzaldehyde has been investigated. In addition to the reduction of the aldehydes, three different reaction patterns have been observed, which depend on the alkenyl, alkyl, and aryl nature of the substituent at the carbonyl group. As a result, the complexes [Os(η5-C5H5)(CO)(η2-PhCH═CH2)(PiPr3)]BF4 (2), [Os(η5-C5H5)(CO)2(PiPr3)]BF4 (3), and [OsH(η5-C5H

  的二氢化-丙酮络合物的反应[OSH 2（η 5 -C 5 H ^ 5）（κ 1 -OCMe 2）（P我镨3）] BF 4（1）朝向肉桂醛，异戊醛和苯甲醛进行了研究。除了醛的还原以外，还观察到三种不同的反应模式，这取决于羰基上取代基的烯基，烷基和芳基性质。其结果是，该配合物[OS（η 5 -C 5 H ^ 5）（CO）（η 2 -PhCH═CH 2）（P我镨3）] BF 4（2），[O的（η 5 -C 5 H ^ 5）（CO）2（P我镨3）] BF 4（3），和[ OSH（η 5 -C 5 H ^ 5） C 6 H 4 C（O）H}（P i Pr 3）] BF 4（6）已被分离和表征，包括X射线结构2。
• 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.