[Os(η5-C5H5)(η2-1,1-diphenyl-2-propyn-1-ol)(P(i)Pr3)]PF6 | 399534-60-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [Os(η5-C5H5)(η2-1,1-diphenyl-2-propyn-1-ol)(P(i)Pr3)]PF6
• 英文别名: cyclopenta-1,3-diene;1,1-diphenylprop-2-yn-1-ol;osmium(2+);tri(propan-2-yl)phosphane;hexafluorophosphate
• CAS: 399534-60-2
• 化学式: C₂₉H₃₈OOsP*F₆P
• 分子量: 768.758
• InChiKey: WAYSPPKNWWQWES-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Os(η5-C5H5)(η2-1,1-diphenyl-2-propyn-1-ol)(P(i)Pr3)]PF6 、 二苯基膦 以 二氯甲烷 为溶剂， 以87%的产率得到[OsH(η5-C5H5)(1,1-diphenyl-2-propyn-1-ol(-1H))(diphenylphosphine)(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
• 作为产物：
  描述：

  thallium(I) hexafluorophosphate 、 (η(5)-cyclopentadienyl)OsCl(triisopropylphosphine)(η(2)-1,1-diphenyl-2-propyn-1-ol) 以 二氯甲烷 为溶剂， 以81%的产率得到[Os(η5-C5H5)(η2-1,1-diphenyl-2-propyn-1-ol)(P(i)Pr3)]PF6
  参考文献：
  名称：

  Cycl-环戊二烯基化学中的两个和四个电子炔烃配体：π⊥ →M相互作用的结果

  摘要：

  络合物OS（η 5 -C 5 H ^ 5）氯{ η 2 -HC⋮CC（OH）R 2 }（P我镨3）（R =苯基（1A）中，Me（1B）），与TlPF反应6至得到[OS（η 5 -C 5 H ^ 5）{ η 2 -HC⋮CC（OH）R 2 }（P我镨3）] PF 6（R =苯基（图2a）中，Me（2B））。1a和2a的结构已经通过X射线衍射确定。数据的比较研究表明，从1a到2a的Os-C（炔烃）距离缩短，而炔键长度几乎保持不变。比较它们的1 H和13 C { 1 H} NMR谱表明，与1a和1b相比，2a和2b的HC⋮质子共振和炔属碳原子的化学位移基本上移向了较低的场。DFT计算是在OS（进行η 5 -C 5 H ^ 5）氯（η 2-HC⋮CR）（PH 3）（R = H（A），R = CH 3（A CH3））和[OS（η 5 -C 5 H ^ 5）（η 2 -HC⋮CR）（PH 3）] +（R

  DOI：

  10.1021/om010645n