[Os(η5-C5H5)(η2-(Z)-CH(CH3)=CHCH3)(κ3-(P,C,C)-[CH2=C(CH3)]P(i)Pr2)]BF4 | 937169-89-6

• 英文名称: [Os(η5-C5H5)(η2-(Z)-CH(CH3)=CHCH3)(κ3-(P,C,C)-[CH2=C(CH3)]P(i)Pr2)]BF4
• CAS: 937169-89-6
• 化学式: BF₄*C₁₈H₃₂OsP
• 分子量: 556.43
• InChiKey: QKRZCAORIWIIBC-NPDUFXBMSA-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：
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反应信息

• 作为反应物：
  描述：

  2-丁炔 、 [Os(η5-C5H5)(η2-(Z)-CH(CH3)=CHCH3)(κ3-(P,C,C)-[CH2=C(CH3)]P(i)Pr2)]BF4 以 二氯甲烷-D2 为溶剂， 生成 [OsH(η5-C5H5)(κ4-(P,C,C,C)-CH2C[CH2C(=CH2)P(i)Pr2]CHCH3)]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：

  2-丁炔 、 [OsH(η5-C5H5)(η3-CH2CHCHPh)(P(i)Pr3)]BF4 以 丙酮 为溶剂， 以56%的产率得到[Os(η5-C5H5)(η2-(Z)-CH(CH3)=CHCH3)(κ3-(P,C,C)-[CH2=C(CH3)]P(i)Pr2)]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