Ruthenium(II)(η5-indenyl)hydride[1,2-bis(diphenylphosphino)ethane] | 199189-24-7

• 英文名称: Ruthenium(II)(η5-indenyl)hydride[1,2-bis(diphenylphosphino)ethane]
• 英文别名: Ru(H)(η(5)-indenyl)(1,2-bis(diphenylphosphino)ethane)；ruthenium(II) hydride (η5-indenyl)(dppe)；(indenyl) [1,2-bis(diphenylphosphino)ethane]ruthenium hydride
• CAS: 199189-24-7
• 化学式: C₃₅H₃₂P₂Ru
• 分子量: 615.657
• InChiKey: OVTFOQXGIPUFRN-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：

  Ruthenium(II)(η5-indenyl)hydride[1,2-bis(diphenylphosphino)ethane] 、 丙炔酸甲酯 以 乙醚 为溶剂， 以70%的产率得到Ru(C(CO2Me)=CH2)(η(5)-indenyl)(1,2-bis(diphenylphosphino)ethane)
  参考文献：
  名称：

  炔烃插入茚基钌（II）氢化物配合物的Ru-H键中的插入反应。苯乙炔与[期RuH反应机理（η 5-C 9 H 7）（dppm）]（dppm =双（二苯基膦基）甲烷）

  摘要：

  茚基配合物[RUX（η 5 -C 9 ħ 7）（DPPM）]（DPPM =双（二苯基膦基）甲烷，X = H，d）用苯乙炔反应，得到的产物顺式加成的[Ru {（ë） - CH CXPh}（η 5 -C 9 ħ 7）（DPPM）]在甲苯中，在温度范围40-80℃。茚基配合物[期RuH（η 5 -C 9 ħ 7）LL ']（L = L'= PME 2 Ph值; L = PPH 3，L '= PME 2 Ph值; L = PPH 3，L'= PME 3 ; LL” = DPPE）和[期RuH（η 5 -Me 3 ç9 ħ 4）（CO）（PPH 3）]和环戊二烯基配合物[期RuH（η 5 -C 5 H ^ 5）（DPPM）]不与光子晶体⋮CH发生反应，即使在更加强制的条件。的配合物[期RuH（η 5 -C 9 ħ 7）LL ']（LL'= DPPE; LL '= DPPM; L = L'= PME 2

  DOI：

  10.1021/om970489d
• 作为产物：
  描述：

  [(η6-indene)(hydrido)(((C6H5)2PCH2)2)ruthenium]CF3SO3 在 (C₂H₅)3N 作用下， 以 氘代四氢呋喃 为溶剂， 生成 Ruthenium(II)(η5-indenyl)hydride[1,2-bis(diphenylphosphino)ethane]
  参考文献：
  名称：

  Protonation of η⁵-Indenyl Ruthenium Hydride Complexes (η⁵-C₉H₇)Ru(L₂)H and η⁵−η⁶ Haptotropic Rearrangement. X-ray Crystal Structures of (η⁵-C₉H₇)Ru(dppm)H and [(η⁶-C₉H₈)Ru(dppp)H]⁺

  摘要：

  Protonation of indenyl complexes (eta(5)-C9H7)Ru(dppm)H and (eta(5)-C9H7)Ru(PPh3)(2)H with CF3-SO3H or HBF4. Et2O at -60 degrees C gives the eta(2)-dihydrogen complex [(eta(5)-C9H7)Ru(dppm)(H-2)](+) and the dihydride [(eta(5)-C9H7)Ru(PPh3)(2)H-2](+), respectively. Upon warming to room temperature, proton shift from the eta(2)-H-2 ligand of the former to the indenyl ligand and subsequent migration of the metal fragment from the five-membered ring to the six-membered ring of the indene Ligand results in the formation of the eta(6)-indene complex [(eta(6)-C9H8)Ru(dppm)H](+). The PPh3 analogue[(eta(6)-C9H8)Ru(PPh3)(2)H](+) is formed in a similar fashion, but in this case, the proton shift is from Ru-H to the indenyl ligand. Low-temperature acidification of (eta(5)-C9H7)Ru(dppe)H and (eta(5)-C9H7)Ru(dppp)H yield mixtures of eta(2)-dihydrogen complex and dihydride in both cases. Similar to the dppm and PPh3 analogues, eta(6)-indene complexes [(eta(6)-C9H8)Ru(dppe)H](+) and [(eta(6)-C9H8)Ru(dppp)H](+) are generated upon warming solutions of the eta(2)-dihydrogen complex/dihydride mixtures to room temperature. In the dppp system, the eta(5) --> eta(6) haptotropic rearrangement only occurs after the eta(2)-dihydrogen complex --> dihydride tautomerization is nearly completed, whereas in the dppe system the two processes seem to occur simultaneously. The parent hydride complexes (eta(5)-C9H7)Ru(L-2)H can be regenerated upon deprotonation of the eta(6)-indene complexes with Et3N. Crystal structures of (eta(5)-C9H7)-Ru(dppm)H and [(eta(6)-C9H8)Ru(dppp)H](+) have been determined by X-ray crystallography; both complexes have three-legged piano-stool structures.

  DOI：

  10.1021/om000266e

文献信息

• η5-Indenylruthenium(II) hydride complexes: synthesis and protonation reactions
  作者：M.Pilar Gamasa、J Gimeno、Covadonga González-Bernardo、B.M Martı́n-Vaca、Javier Borge、Santiago Garcı́a-Granda

  DOI：10.1016/s0020-1693(02)01457-3

  日期：2003.4

  Hydride complexes [RuH(η5-1,2,3-C9R3R′4)LL′] (R=R′=H, LL′=dppm (1), dppe (2); L=L′=PMe2Ph (3); L=PPh3, L′=PMe3 (4), PMe2 Ph (5), PMePh2 (6); L=CO, L′=PiPr3 (7); R=Me, R′=H, LL′=dppm (8); L=CO, L′=PPh3 (9), PiPr3 (10); R=R′=Me, L=CO, L′=PiPr3 (11)) have been prepared by the reaction of complexes [RuX(η5-1,2,3-C9R3R′4)LL′] (X=Cl, Br) with an excess of NaOMe in methanol (reflux or room temperature). Protonation

  氢化物配合物[RuH（η5-1,2,3-C9R3R'4）LL']（R = R'= H，LL'= dpPM（1），dppe（2）; L = L'= PMe2Ph（3） ; L = PPh3，L'= PMe3（4），PMe2 Ph（5），PMePh2（6）; L = CO，L'= PiPr3（7）; R = Me，R'= H，LL'= dpPM（ 8）； L ＝ CO，L′＝ PPh 3（9），PiPr 3（10）； R ＝ R′＝ Me，L ＝ CO，L′＝ PiPr 3（11））是通过配合物[RuX（ η5-1,2,3-C9R3R'4）LL']（X = Cl，Br）和过量的NaOMe的甲醇溶液（回流或室温）。在Et2O中用HBF4·OEt2将氢化物络合物[RuH（η5-C9H7）（PPh3）L]（L = PPh3（12），PMe3（4））质子化，生成二氢化物络合物[RuH2（η5- ）（PPh3）