[(η4-1,5-cyclooctadiene)Rh(η5,κ2-P,N-1-P-i-Pr2-2-NMe2-indenyl)Ru(η5-C5Me5)]BF4 | 960058-61-1

• 英文名称: [(η4-1,5-cyclooctadiene)Rh(η5,κ2-P,N-1-P-i-Pr2-2-NMe2-indenyl)Ru(η5-C5Me5)]BF4
• CAS: 960058-61-1
• 化学式: BF₄*C₃₅H₅₂NPRhRu
• 分子量: 808.558
• InChiKey: INJZZNMIRYDWOJ-ISVFTUMHSA-N

反应信息

• 作为产物：
  描述：

  (κ2-P,N-1-P-i-Pr2-2-NMe2-indenyl)Ru(η5-C5Me5) 、 silver tetrafluoroborate 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 以 四氢呋喃 为溶剂， 以96%的产率得到[(η4-1,5-cyclooctadiene)Rh(η5,κ2-P,N-1-P-i-Pr2-2-NMe2-indenyl)Ru(η5-C5Me5)]BF4
  参考文献：
  名称：

  New Racemic Planar-Chiral Metalloligands Derived from Donor-Substituted Indenes:  A Synthetic, Structural, and Catalytic Investigation

  摘要：

  The synthesis and characterization of a new family of (eta(5)-indenyl)MLn complexes (MLn = Mn(CO)(3), Cp*Ru, or Cp*Fe; Cp* = eta(5)-C5Me5) derived from 3-(PPr2)-Pr-i-indene, 1-(PPr2)-Pr-i-2-NMe2-indene (1a[H]), or 1-P(S)Pr-i(2)-2-NMe2-indene (1b[H]) are described. Lithiation of 1b[H] followed by treatment with BrMn(CO)(5), 0.25 equiv of [Cp*RuCl](4), or Cp*Li/FeCl2 provided the corresponding (eta(5)-1b)MLn complexes (MLn = Mn(CO)(3), 2a, 96%; Cp*Ru, 2b, 87%; or Cp*Fe, 2c, 55%). Similarly, treatment of 1a[Li] with 0.25 equiv of [Cp*RuCl](4) or Cp*Li/FeCl2 provided the corresponding (eta(5)-1a)MLn complexes (MLn = Cp*Ru, 3b, 74%; or Cp*Fe, 3c, 62%). Whereas combination of 3b and 0.5 equiv of [(COD)RhCl](2) afforded [(COD)Rh(kappa(2) -P,N-3b)]Cl-+(-) ([4b]Cl-+(-); 49% isolated yield), under similar conditions 3c was observed to undergo a decomposition reaction resulting in the formation of the zwitterionic complex (COD)Rh(kappa(2) -P,N-1a) (5; COD = eta(4)- 1, 5-cyclooctadiene). Each of 3a-c was observed to react cleanly with [(COD)Rh(THF)(2)]+BF4- (prepared in situ) to give the corresponding [(COD)Rh(kappa(2)-P,N-3a-c)]+BF4- complex ([4a-c]+BF4-; 87%, 96%, and 89% isolated yield, respectively). Whereas lithiation of 3-(PPr2)-Pr-i-indene followed by the addition of BrMn(CO)5 generated a complex mixture of products, similar reactions employing 0.25 equiv of [Cp*RuCl](4) Or Cp*Li/FeCl2 afforded 6b or 6c in 98% and 43% yield, respectively. Treatment of 6b with 0.5 equiv of [(COD)RhCl](2) allowed for the isolation of (COD)RhCl(kappa(1)-P-6b) 7 in 96% isolated yield. Each of [4a-c]+BF4- proved to be an active catalyst for addition of pinacolborane to styrene, with the observed regioselectivity being dependent on the nature of the eta(5)-coordinated metal fragment, as well as the solvent employed. Single-crystal X-ray diffraction data for 2a, 2b, 2c, 3b, [4c]+BF4-, and 7 are provided.

  DOI：

  10.1021/om700832f