Rh(CF₃COCHCOFc)(COD) | 213037-34-4

• 英文名称: Rh(CF₃COCHCOFc)(COD)
• 英文别名: Rh(CF₃COCHCOferrocenyl)(1,5-cyclooctadiene)；[Rh(1,5-cyclooctadiene)(ferrocenoyltrifluoroacetonato)]；[Rh(FcCOCHCOCF3)(1,5-cyclooctadiene)]
• CAS: 213037-34-4
• 化学式: C₂₂H₂₂F₃FeO₂Rh
• 分子量: 534.163
• InChiKey: FCXFMOBWKBJNPT-KJWGIZLLSA-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：

  Rh(CF₃COCHCOFc)(COD) 、 一氧化碳 以 丙酮 为溶剂， 以83%的产率得到Rh(ferrocenylCOCHCOCF3)(carbonyl)2
  参考文献：
  名称：

  含二茂铁的铑（I）和铑（III）的合成和表征

  摘要：

  [Rh（FcCOCHCOR）（CO）2 ]和[Rh（FcCOCHCOR）（CO）（PPh 3）]类型的新β-二酮铑（I）配合物的合成，其中Fc =二茂铁基且R = Fc，C 6描述了H 5，CH 3和CF 3。1 H，13 C和31 P NMR数据显示，对于每种非对称β-二酮单羰基铑（I）络合物，溶液中均存在两种异构体。与平衡反应中的这两种异构体有关的平衡常数K c与浓度无关，但与温度和溶剂有关。Δ - [R G ^，Δ - [R ħ和Δ ř小号这个平衡值已被确定，并在规模迪姆罗极性溶剂之间的线性关系和ķ Ç存在。RhP键长，d之间（RhP）和的关系，31个P NMR峰位置，以及耦合常数1 Ĵ（31 P 103的Rh）已被量化，以允许近似d的计算（RhP）价值观。在d的变化（RhP）用于铑[Rh（RCOCHCOR'）（CO）（PPH 3）]配合物也被与终端相关β-二酮盐的R基团的电负性基团（戈迪刻度）反式到PPH

  DOI：

  10.1016/s0020-1693(01)00731-9
• 作为产物：
  描述：

  di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium 、 (Z)-1-ferrocenyl-4,4,4-trifluoro-2-hydroxy-2-en-1-butaone 以 N,N-二甲基甲酰胺 为溶剂， 以87%的产率得到Rh(CF₃COCHCOFc)(COD)
  参考文献：
  名称：

  含二茂铁基的β-二酮：合成，结构方面，p K a 1值，基团电负性和与铑（I）的络合

  摘要：

  1-二茂铁基-4,4,4-三氟丁烷-1,3-二酮（二茂铁酰基三氟丙酮，Hfctfa，p K a 1  = 6.53±0.03），4,4,4-三氯-1-二茂铁基丁烷-1,3-二酮（三氯 二茂铁基丙酮，Hfctca，p K a 1 = 7.15±0.02），1-二茂铁基丁烷-1,3-二酮（二茂铁基丙酮，Hfca，p K a 1  = 10.01±0.02），1-二茂铁基-3-苯基丙烷-1,3-二酮（苯甲酰二茂铁酰基甲烷，Hbfcm，p K a 1  = 10.41±0.02）和1,3-二茂铁基丙烷-1,3-二酮（二茂铁酰基甲烷，Hdfcm，p K a 1 通过在酰胺钠，乙醇钠或二异丙基氨基锂的影响下，将乙酰基二茂铁与适当的酯进行克莱森缩合反应，制得13.1±0.1）。从线性β-二酮p K a 1-基团电负性关系以及线性甲酯IR羰基拉伸频率-基团电负性关系推断，二茂铁基的基团电负性为1.87（高迪标度）。通过用[Rh

  DOI：

  10.1039/a802398k

文献信息

• Kinetics of substitution of ferrocenyl-containing β-diketonato ligands by phenanthroline from β-diketonato-1,5-cyclooctadienerhodium(I) complexes
  作者：Theunis G. Vosloo、W.C. (Ina) du Plessis、Jannie C. Swarts

  DOI：10.1016/s0020-1693(01)00805-2

  日期：2002.3

  Second-order rate constants, k(2), for the substitution of the ferrocene-containing beta-diketonato ligands FeCOCHCOR- with R = CF3 (ferrocenoyltrifluroacetonato, fctfa, pK(a) 6.56), CCl3 (ferrocenoyltrichloroacetonato. fetca, 7.13), CH3 (ferrocenoylacatonato, fca, 10.01), Ph (anion of benzoylferrocenoylmethane, bfcm. 10.41) and Fe (anion of diferrocenoylmethane, dfcm, 13.1) (Ph = phenyl, Fc = ferrocenyl, values in brackets are the pK(a) values of the free beta-diketones) from the complexes [Rh(cod)(FcCOCHCOR)] with 1,10-phenanthroline (phen, cod = 1,5-cyclooctadiene) at 25 degreesC were found to be 560 (R = CF3), 1370 (CCl3), 30 (Ph), 18 (CH3) and 7.0 dm(3) mol(-1) s(-1) (Fc), respectively. The temperature dependence of each reaction was determined and the large negative values obtained for activation, DeltaS* < -100 J K (1) mol (1) for all but R = CCl3 (DeltaS(CCl3)* = -81 J K-1 mol(-1)), suggests an associative substitution mechanism. The rate law of the reaction was found to be R = k(s) + k(2)[phen]}[Rh(cod)(FcCOCHCOR)]. Since the solvent-associated rate constant k(s) approximate to 0 for all R except Ph (k(s,R Ph) = 0.06 s(-1)) the solvent. methanol. plays a limited role in the reaction. Results are interpreted to imply that the rate-determining step during substitution is breaking of an Rh-O bond and not the formation of an Rh-N bond. The role of beta-diketone pK(a), and group electronegativity, chi, of each R group on the rate of substitution are also discussed. (C) 2002 Elsevier Science B.V. All rights reserved.
• Synthetic, electrochemical and structural aspects of a series of ferrocene-containing dicarbonyl β-diketonato rhodium(I) complexes
  作者：Jeanet Conradie、T. Stanley Cameron、Manuel A. S. Aquino、Gert J. Lamprecht、Jannie C. Swarts

  DOI：10.1016/j.ica.2005.02.010

  日期：2005.5

  Treatment of [Rh(beta-diketonato)(cod)] with CO resulted in better yields of [Rh(FcCOCHCOR)(CO)(2)] than by treating [Rh(Cl)(CO)(2)](2) with FcCOCH(2)COR, R = CF3 (Hfctfa), CH3 (Hfca), Ph (Hbfcm, Ph = phenyl) and Fc (Hdfcm, Fc ferrocenyl). The single crystal structure of the fctfa rhodium(I) complex [C16H10F3FeO4Rh], monoclinic, C 2/c(15), a 13.266(3) angstrom, b = 19.553(3) angstrom, c = 13.278(3) angstrom, beta = 100.92(2)degrees, Z = 8 showed both rotational and translational displacement disorders for the CF3 group. An electrochemical study revealed that the formal reduction potential, E-0 ', for the electrochemically reversible one electron oxidation of the ferrocenyl group varied between 0.304 (for the fctfa complex) and 0.172 V (for the dfcm complex) versus Fc/ Fc(+) in a manner that could be directly traced to the group electronegativities, chi(R), of the R groups on the beta-diketonato ligands, as well as to the pK '(a) values of the free beta-diketones. Anodic peak potentials, E-pa.Rh,E- for the dominant cyclic voltammetry peak asso- ciated with rhodium(l) oxidation were between 0.718 (bfcm complex) and 1.022 V (dfcm complex) versus Fc/Fc '. Coulometric experiments implicated a second, much less pronounced anodic wave for the apparent two-electron Rh-I oxidation that overlaps with the ferrocenyl anodic wave and that the redox processes associated with these two Rh-I oxidation waves are in slow equilibrium with each other. (c) 2005 Elsevier B.V. All rights reserved.