OsH(η5-C5H5)(=C=CHC(O)CH3)(P(i)Pr3) | 871576-67-9

• 英文名称: OsH(η5-C5H5)(=C=CHC(O)CH3)(P(i)Pr3)
• CAS: 871576-67-9
• 化学式: C₁₈H₃₁OOsP
• 分子量: 484.617
• InChiKey: INZIDXQMLGMGSY-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  Os(η5-C5H5)(CHCHC(O)CH3)(P(i)Pr3) 、 OsH(η5-C5H5)(=C=CHC(O)CH3)(P(i)Pr3) 在 HBF₄*(C₂H₅)2O 作用下， 以 二氯甲烷-D2 为溶剂， 生成 [OsH(η5-C5H5)(CHCHC(O)CH3)(P(i)Pr3)](1+)
  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：

  [OsH(η5-C5H5)(CHCHC(O)CH3)(P(i)Pr3)]PF6 在 NaOCH₃ 作用下， 以 四氢呋喃 为溶剂， 生成 Os(η5-C5H5)(CHCHC(O)CH3)(P(i)Pr3) 、 OsH(η5-C5H5)(=C=CHC(O)CH3)(P(i)Pr3)
  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