Os(η(5)-C5H5)Cl(η(2)-CH2=CHC(O)CH3)(PiPr3) | 196520-53-3

• 英文名称: Os(η(5)-C5H5)Cl(η(2)-CH2=CHC(O)CH3)(PiPr3)
• 英文别名: Os(η5-C5H5)Cl(η2-methyl vinyl ketone)(P(i)Pr3)
• CAS: 196520-53-3
• 化学式: C₁₈H₃₂ClOOsP
• 分子量: 521.078
• InChiKey: MLDHJFXHFONEQG-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  thallium(I) hexafluorophosphate 、 Os(η(5)-C5H5)Cl(η(2)-CH2=CHC(O)CH3)(PiPr3) 以 二氯甲烷 为溶剂， 以82%的产率得到[OsH(η5-C5H5)(CHCHC(O)CH3)(P(i)Pr3)]PF6
  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：

  (η(5)-cyclopentadienyl)OsCl(triisopropylphosphine)2 、 丁烯酮 以 甲苯 为溶剂， 以83%的产率得到Os(η(5)-C5H5)Cl(η(2)-CH2=CHC(O)CH3)(PiPr3)
  参考文献：
  名称：

  迈尔络合物OsH 2 Cl 2（P i Pr 3）2作为制备新的环戊二烯基os化合物的前体

  摘要：

  的六配位配合物OSH 2氯2（P我镨3）2（1）反应以cyclopentadienylthallium给OS（η 5 -C 5 H ^ 5）氯（P我镨3）2（2）。在甲醇和丙酮中，2使氯配体解离，得到的金属片段能够活化三异丙基膦的甲基CH键，可以通过添加NaPF 6或TlPF 6将其分离为PF 6盐。。的1:10混合物的治疗2和NaBH 4在甲苯用1.0毫升甲醇，得到OSH（η的5 -C 5 H ^ 5）（P我镨3）2（4），其通过与HBF质子化4 ·OET 2产率[OSH 2（η 5 -C 5 H ^ 5）（P我镨3）2 ] BF 4（5）。在戊烷中，复杂的2种发生反应与亚磷酸三甲酯，得到OS（η 5 -C 5H 5）Cl {P（OMe）3 }（P i Pr 3）（6）。类似地，除了甲苯溶液甲基乙烯基酮和乙炔二的2产生一个膦配位体从位移2和Os的形成（η 5 -C 5 H ^ 5）氯{η

  DOI：

  10.1021/om970237c