[Rh(1,5-cyclooctadiene)(1,10-phenanthroline)](1+) | 47248-45-3

• 英文名称: [Rh(1,5-cyclooctadiene)(1,10-phenanthroline)](1+)
• CAS: 47248-45-3
• 化学式: C₂₀H₂₀N₂Rh
• 分子量: 391.298
• InChiKey: WZZOOKUWODSLFD-GHDUESPLSA-N

计算性质

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

反应信息

• 作为产物：
  描述：

  1,10-菲罗啉 、 [Rh(1,5-cyclooctadiene)(tris(methylthio)(bis(acetyl)methylthio)tetrathiafulvalene(-1H))] 以 methanol 为溶剂， 生成 [Rh(1,5-cyclooctadiene)(1,10-phenanthroline)](1+)
  参考文献：
  名称：

  含铑（I）的第一个含四硫富富瓦烯的β-二酮酮配合物的合成，取代动力学和电化学

  摘要：

  包含在次甲基位置（3位），[Rh（cod）（H 3 CCOC {S-TTF-（MeS ）3 } COCH 3）]（3）或终点位置（1位），报告了[Rh（cod）{（Me 3 -TTF）COCHCOCH 3 }]（4）。β-二酮基取代位置对含TTF的β-二酮基配体被3和4的1,10-菲咯啉取代以生成[Rh（cod）（phen）] +的动力学影响以及的电化学性质3和4，进行了调查。发现甲醇中的二阶取代速率常数k 2几乎与取代位置无关，其中4（k 2 = 2.09×10 3 dm 3 mol -1 s -1）的反应速度几乎是3的两倍。。仅在k s = 42 s -1的4个中观察到替代机制中的可观溶剂途径。提出了两个取代反应的完整机理。CH 2中3和4的电化学Cl 2 /0.10 mol dm -3 [N（n Bu）4 ] [B（C 6 F 5）4 ]显示出三个氧化还原过程。这些中的两个是电化学可

  DOI：

  10.1021/ic901676e

文献信息

• Kinetics of the substitution of acetylacetone in acetylactonato-1,5-cyclooctadienerhodium(I) by derivatives of 1,10-phenantrholine and 2,2′-dipyridyl
  作者：J.G. Leipoldt、G.J. Lamprecht、E.C. Steynberg

  DOI：10.1016/0022-328x(91)83069-g

  日期：1991.1

  [Rh(acac)(COD)] and various derivatives of 1,10-phenanthroline and 2,2′-dipyridyl in MeOH to give [Rh(NN)(COD)]+ has been studied. The observed rate law is T = k [Rh(acac)(COD)[NN]. The large negative values for the entropy of activation suggest an associative mechanism. The values of the second-order rate constants vary only from 12.4 to 29.0 M−1 s−1 at 25°C for a pKa range of the derivatives of phenanthroline

  研究了[Rh（acac）（COD）]与1,10-菲咯啉和2,2'-联吡啶在甲醇中的各种衍生物之间的反应，得到[Rh（NN）（COD）] +。观测到的速率定律是T = k [Rh（acac）（COD）[NN]。激活熵的大负值表明存在一种缔合机制。二阶速率常数的值仅改变从12.4到29.0中号-1 S-1在25℃下为AP ķ一个范围菲咯啉从3.57到6.31的衍生物的，指示打入配体的碱度起着次要角色。的高得多的值ķ用于与2,2'-联吡啶的反应（124中号在25°C下-1 s-1）归因于2,2'-联吡啶在缔合机理中的较低刚性。
• 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.