(1,5-cyclooctadiene)(hexafluoroacetylacetonato)rhodium(I) | 32610-47-2

• 英文名称: (1,5-cyclooctadiene)(hexafluoroacetylacetonato)rhodium(I)
• 英文别名: [(cod)Rh(hfacac)]
• CAS: 32610-47-2
• 化学式: C₁₃H₁₃F₆O₂Rh
• 分子量: 418.141
• InChiKey: VWOKLYTZDGAHHY-GCOBPYNFSA-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：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (1,5-cyclooctadiene)(hexafluoroacetylacetonato)rhodium(I) 、 1,2-双(二苯基膦)乙烷 以 四氢呋喃 为溶剂， 生成 bis(1,2-bis(diphenylphosphino)ethane)rhodium(I) hexafluoroacetylacetonate
  参考文献：
  名称：

  Synthesis and structural features of complexes [(P^{<FONT FACE="WP MathA">1</FONT>}P)₂Rh][hfacac] containing hexafluoroacetyl- acetonate as a noncoordinating anion

  摘要：

  The synthesis and characterization of complexes [(P P-boolean AND)(2)Rh][hfacac] ((PP)-P-boolean AND = chelating bidentate phosphine ligand R2P(CH2)(n)PR2 (2a-g), hfacac = hexafluoroacetylacetonate anion) (4) is reported. The molecular structures of 4a (R = Ph, n = 1) and 4f (R = Cy, n = 2) in the solid state were determined by single-crystal X-ray diffraction. The complexes crystallize in the monoclinic space groups C2/c (No. 15) and P2(1)/n (No. 14), respectively. No coordinative interaction between the rhodium center of the cation [((PP)-P-boolean AND)(2)Rh](+) (4a(+), 4f(+)) and the hfacac anion is evident in either cases. In the crystal structure of 4a, hydrogen bonds between the oxygen atoms of the hfacac anion and methylene protons of the CH2 bridges of the phosphine ligand lead to highly symmetric chains of regularly alternating cations and anions. The coordination geometry around the rhodium center in 4a(+) is ideally square-planar, whereas 4f(+) is significantly distorted towards a tetrahedron with an angle between the two P2Rh moieties of 18.6 degrees. The cation 4b(+) (R = Cy, n = 1) was investigated in form of the tetrafluoroborate salt for comparison. The compound [{Cy2P(CH2)PCy2}(2)Rh][BF4] crystallizes as a THF solvate (4b ) in the triclinic space group P (1) over bar (No. 2) containing ideally square-planar [((PP)-P-boolean AND)(2)Rh](+) cations.

  DOI：

  10.1139/cjc-79-5-6-642

文献信息

• Mechanistic aspects of hydrogen addition during enantioselective rhodium-catalysed reduction of CC double bonds with formic acid/triethylamine or molecular hydrogenBased on the presentation given at Dalton Discussion No. 4, 10–13th January 2002, Kloster Banz, Germany.
  作者：Susanne Lange、Walter Leitner

  DOI：10.1039/b108774f

  日期：2002.2.15

  The use of monodeuterated formic acid isotopomers shows that the incorporation from the hydridic formyl position occurs preferentially at the terminal end of the double bond (C-3) whereas the protic hydrogen is directed either in the higher substituted olefinic (C-2) or the methylene (C-1) position. Control experiments using mesaconic (2) and citraconic (3) acids demonstrate that double bond migration

  氘标记实验表明，在均相催化的C C键过程中，氢的添加方式显着不同减少分子氢（氢化）制备衣康酸衍生物1a-d或甲酸/三乙胺 （转移 氢化）。常规情况下，所有底物在双键上预期会出现两个氢原子的邻位加成氢化，而氘的模式主要取决于转移过程中β（或烯丙基）位置的羧基的性质 氢化。连位此外，观察到只在衣康酸的情况下，图1A和α-methylitaconate 1C，而1,3-加成优选与二甲基衣康酸酯1b和β-甲基衣康酸酯1d一起使用。在此过程中也会形成大量的多氘代产物氢化 和转移 氢化。监测氘随时间变化的模式表明，氘加扰是多氘化的原因，而不是加成模式的改变。单氘化甲酸异位异构体的使用表明从氢化物中引入甲酰 位置优先出现在双键（C-3）的末端，而质子氢则直接在高级取代的烯烃（C-2）或 亚甲基（C-1）位置。使用中康酸（2）和柠康酸（3）的对照实验表明，在反应条件下1a-d中的双键迁移可忽略不计。这些结果最好在通用机制的基础上合理化。氢化