[Rh(2-thenoyltrifluoroacetonate)(CO)(PPh3)] | 67415-33-2

• 英文名称: [Rh(2-thenoyltrifluoroacetonate)(CO)(PPh3)]
• 英文别名: [Rh(CO)(2-thenoyltrifluoroacetonate)(PPh3)]；[Rh(CO)(tta)(PPh3)]
• CAS: 67415-33-2；95120-57-3；192371-51-0
• 化学式: C₂₇H₁₉F₃O₃PRhS
• 分子量: 614.387
• InChiKey: AIHCCHZZCBYFFB-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：

  碘甲烷 、 [Rh(2-thenoyltrifluoroacetonate)(CO)(PPh3)] 以 氘代氯仿 为溶剂， 生成 [Rh(CO)(2-thenoyltrifluoroacetonate)(PPh3)(CH3)I]
  参考文献：
  名称：

  A kinetic study of the oxidative addition of methyl iodide to [Rh((C4H3S)COCHCOCF3)(CO)(PPh3)] utilizing UV/vis and IR spectrophotometry and 1H, 19F and 31P NMR spectroscopy. Synthesis of [Rh((C4H3S)COCHCOCF3)(CO)(PPh3)(CH3)(I)]

  摘要：

  IR and UV/vis spectrophotometric and H-1, F-19 and P-31 NMR spectroscopic techniques have been utilized to study the kinetics of oxidative addition of CH3I to [Rh(tta)(CO)(PPh3)] with Htta = (C4H3S)COCH2COCF3 = 2-thenoyltrifluoroacetone. Two definite reactions steps involving isomers of at least two distinctly different classes of Rh-III-alkyl and a Rh-III-acyl species were observed. NMR spectroscopy revealed that each reaction product exists in solution of two observable isomers in equilibrium with each other. The observed rate of oxidative addition of iodomethane to the different [Rh(tta)(CO)(PPh3)] isomers was the same, but the rate of formation of the two isomers of the final Rh-III-alkyl2 reaction product, [Rh(tta)(CO)(CH3)(PPh3)(I)], differs. Results provided the following reaction mechanism.[GRAPHICS]The equilibrium K-2 was fast enough to be maintained during the [Rh(tta)(CO)(PPh3)] depletion in the first reaction step and during the Rh-III-alkyl2 formation in the second reaction step. The molecular formulae of all the Rh-III-alkyl and Rh-III-acyl species are [Rh(tta)(CH3)(CO)(PPh3)(I)] and [Rh(tta)(COCH3)(PPh3)(I)], respectively, but the geometries are different due to different co-ordination positions of the ligands. The final Rh-III-alkyl2 reaction product is isolated and characterized. (c) 2007 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2007.07.010
• 作为产物：
  描述：

  三苯基膦 、 [Rh(2-thenoyltrifluoroacetonate)(CO)2] 以 正己烷 为溶剂， 以40.1%的产率得到[Rh(2-thenoyltrifluoroacetonate)(CO)(PPh3)]
  参考文献：
  名称：

  A kinetic study of the oxidative addition of methyl iodide to [Rh((C4H3S)COCHCOCF3)(CO)(PPh3)] utilizing UV/vis and IR spectrophotometry and 1H, 19F and 31P NMR spectroscopy. Synthesis of [Rh((C4H3S)COCHCOCF3)(CO)(PPh3)(CH3)(I)]

  摘要：

  IR and UV/vis spectrophotometric and H-1, F-19 and P-31 NMR spectroscopic techniques have been utilized to study the kinetics of oxidative addition of CH3I to [Rh(tta)(CO)(PPh3)] with Htta = (C4H3S)COCH2COCF3 = 2-thenoyltrifluoroacetone. Two definite reactions steps involving isomers of at least two distinctly different classes of Rh-III-alkyl and a Rh-III-acyl species were observed. NMR spectroscopy revealed that each reaction product exists in solution of two observable isomers in equilibrium with each other. The observed rate of oxidative addition of iodomethane to the different [Rh(tta)(CO)(PPh3)] isomers was the same, but the rate of formation of the two isomers of the final Rh-III-alkyl2 reaction product, [Rh(tta)(CO)(CH3)(PPh3)(I)], differs. Results provided the following reaction mechanism.[GRAPHICS]The equilibrium K-2 was fast enough to be maintained during the [Rh(tta)(CO)(PPh3)] depletion in the first reaction step and during the Rh-III-alkyl2 formation in the second reaction step. The molecular formulae of all the Rh-III-alkyl and Rh-III-acyl species are [Rh(tta)(CH3)(CO)(PPh3)(I)] and [Rh(tta)(COCH3)(PPh3)(I)], respectively, but the geometries are different due to different co-ordination positions of the ligands. The final Rh-III-alkyl2 reaction product is isolated and characterized. (c) 2007 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2007.07.010

文献信息

• The crystal structure of tropolonatocarbonyltriphenylphosphinerhodium(I)
  作者：J.G. Leipoldt、L.D.C. Bok、S.S. Basson、H. Meyer

  DOI：10.1016/s0020-1693(00)88893-3

  日期：1980.1
• Trans effect in β-diketone complexes of rhodium(I)
  作者：J.G. Leipoldt、L.D.C. Bok、S.S. Basson、T.I.A. Gerber

  DOI：10.1016/s0020-1693(00)94664-4

  日期：1979.1
• Stereochemistry of the reaction products of the oxidative addition reaction of methyl iodide to [Rh((C4H3S)COCHCOR)(CO)(PPh3)]: A NMR and computational study. R=CF3, C6H5, C4H3S
  作者：Marrigje M. Conradie、Jeanet Conradie

  DOI：10.1016/j.ica.2008.04.046

  日期：2009.1

  A NMR study of the reaction mixture of the square planar [Rh((C4H3S) COCHCOR)(CO)(PPh3)] complex and CH3I, where R = CF3, C6H5 or C4H3S, revealed that two types of alkyl and one (R = CF3) or two (R = C6H5 or C4H3S) types of acyl species exist in the system. Two isomers of each species with an unsymmetrical beta-diketonato ligand were observed. H-1-H-1 NOESY NMR unambiguously showed that the PPh3 group is in the apical position in the more stable Rh-III-alkyl product. Theoretical computations of the equilibrium geometry of the possible reaction products, consistent with experimental observations, revealed that the. first alkyl product results from trans addition to Rh-I and that the second thermodynamic alkyl product adopts an octahedral geometry with the PPh3 group and the iodide above and below the square planar plane. Theoretical computations also revealed that the thermodynamic acyl product adopts a square-pyramidal geometry with the COCH3 group in the apical position. (C) 2008 Elsevier B.V. All rights reserved.