[Os(η5-C5H5)(η2-1,1-diphenyl-2-propyn-1-ol)(CO)(P(i)Pr3)]PF6 | 811434-22-7

• 英文名称: [Os(η5-C5H5)(η2-1,1-diphenyl-2-propyn-1-ol)(CO)(P(i)Pr3)]PF6
• CAS: 811434-22-7
• 化学式: C₃₀H₃₈O₂OsP*F₆P
• 分子量: 796.768
• InChiKey: NEUNTAKATWWQHK-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：
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反应信息

• 作为产物：
  描述：

  [Os(η5-C5H5)(η2-1,1-diphenyl-2-propyn-1-ol)(P(i)Pr3)]PF6 、 一氧化碳 以 二氯甲烷-D2 为溶剂， 生成 [Os(η5-C5H5)(diphenylallenylidene)(CO)(P(i)Pr3)]PF6 、 [Os(η5-C5H5)(=C=CHC(OH)Ph2)(CO)(P(i)Pr3)]PF6 、 [Os(η5-C5H5)(η2-1,1-diphenyl-2-propyn-1-ol)(CO)(P(i)Pr3)]PF6
  参考文献：
  名称：

  A Four-Electron π-Alkyne Complex as Precursor for Allenylidene Derivatives:  Preparation, Structure, and Reactivity of [Os(η⁵-C₅H₅)(CCCPh₂)L(PⁱPr₃)]PF₆ (L = CO, PHPh₂)

  摘要：

  The pi-alkyne complex [Os(eta(5)-C5H5){eta(2)-HCdropCC(OH)Ph-2}((PPr3)-Pr-i)]PF6 (1), where the alkyne acts as a four-electron donor ligand, reacts with CO to give initially the two-electron pi-alkyne derivative [Os(eta(5)-C5H5){ eta(2)-HCdropCC(OH)Ph2}(CO)((PPr3)-Pr-i)]PF6 (2). In dichloromethane, complex 2 isomerizes into the hydroxyvinylidene [Os(eta(5)-C5H5){=C=CHC(OH)Ph-2}(CO)((PPr3)-Pr-i)]PF6 (3), which dehydrates to afford the allenylidene [Os(eta(5)-C5H5)(=C=C=CPh2)(CO)((PPr3)-Pr-i)]PF6 (4). Complex 1 also reacts with PHPh2. In this case, the reaction initially gives the hydridehydroxyalkynyl intermediate [OsH(eta(5)-C5H5){CdropCC(OH)Ph-2}(PHPh2)((PPr3)-Pr-i)]PF6 (5). Similar to 2, in dichloromethane, complex 5 isomerizes into the hydroxyvinylidene [Os(eta(5)-C5H5){= C=CHC(OH)Ph-2}(PHPh2)((PPr3)-Pr-i)]PF6 (6), which dehydrates to afford [Os(eta(5)-C5H5)(=C=C= CPh2)(PHPh2)((PPr3)-Pr-i)]PF6 (7). In the presence of HPF6, complex 4 isomerizes into [Os(eta(5)-C5H5)(3-phenyl-1-indenylidene)(CO)((PPr3)-Pr-i)]PF6 (8). Under the same conditions, compound 7 affords the dicationic alkenylcarbyne derivative [Os(eta(5)-C5H5)(dropC-CH=CPh2)(PHPh2)((PPr3)-Pr-i)](PF6)(2) (9). The allenylidene ligand of 4 undergoes the addition of carbodiimides to give iminiumazetidinylidenemethyl derivatives. The reaction with N,N'-dicyclohexylcarbodiimide affords [Os(eta(5)-C5H5){CH=CC(Ph)(2)N(Cy)=C=N=C(CH2)(4)CH2}(CO)((PPr3)-Pr-i)]PF6 (10), whereas the reaction with N,N'-diisopropylcarbodiimide leads to [Os(eta(5)-C5H5){CH=CC(Ph)(2)N(Pr-i) =C=N=C(CH3)(2)}(CO)((PPr3)-Pr-i)]PF6 (11). Complex 4 also reacts with methanol and aniline. The addition of methanol to the allenylidene 4 gives [Os(eta(5)-C5H5){C(OCH3)CH=CPh2}(CO)((PPr3)-Pr-i)]PF6 (12), which undergoes deprotonation at the CH=CPh2 group to afford Os(eta(5)-C5H5){C(OCH3)=C=CPh2}(CO)((PPr3)-Pr-i) (13). The addition of aniline leads to [Os(eta(5)-C5H5){C(CH=CPh2)=NHPh}(CO)((PPr3)-Pr-i)]PF6 (14). Treatment of 14 with NaOCH3 gives Os(eta(5)-C5H5){C(CH=CPh2)=NPh}(CO)((PPr3)-Pr-i) (15). Complexes 4, 7, and 8 have been characterized by X-ray diffraction analysis.

  DOI：

  10.1021/om049479k