Rh((CH3CO)2CH)(P(C6H11)3)(η(2)-HCCCO2CH3) | 178211-44-4

• 英文名称: Rh((CH3CO)2CH)(P(C6H11)3)(η(2)-HCCCO2CH3)
• CAS: 178211-44-4
• 化学式: C₂₇H₄₄O₄PRh
• 分子量: 566.523
• InChiKey: HJKZKLJMNHQUMC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  Rh((CH3CO)2CH)(P(C6H11)3)(η(2)-HCCCO2CH3) 、 三环己基膦 以 甲苯 为溶剂， 以34%的产率得到
  参考文献：
  名称：

  Substitution and Oxidative Addition Reactions of the Monoolefin Complex Rh(acac)(cyclooctene)(PCy₃) Including the X-ray Structure Analyses of Rh(acac)(PCy₃)₂ and [Rh(acac){(E)-CHCHCy}(PCy₃)₂]BF₄

  摘要：

  The olefin complex Rh(acac)(cyclooctene)(PCy(3)) (2), which is formed from Rh(acac)(cyclooctene)(2) (1) PCy(3) in nearly quantitative yield, reacts with CO and alkynes RC=CR by ligand displacement to give Rh(acac)(CO)(PCy(3)) (3) and Rh(acac)(eta(2)-RC=CR)(PCy(3)) [R=CO(2)Me (4), Ph (5)], respectively. The bis(phosphine) compound Rh(acac)(PCy(3))(2) (6) cannot be prepared directly from 2 and excess PCy(3) but via Rh(acac)(eta(2)-HC=CCO(2)Me)(PCy(3)) (7) as intermediate. The X-ray crystal structure analysis of 6 reveals that the rhodium is coordinated in a distorted square-planar manner with O-Rh-O and P-Rh-P bond angles of 85.9(1) and 105.63(4)degrees. Compound 2 reacts with H-2 in the presence of PCy(3) to yield Rh(acac)H-2(PCy(3))(2) (8) and with HC=CR/PCy(3) to give Rh(acac)H(C=CR)(PCy(3))(2) [R=Ph (9), Cy (10), SiMe(3) (11)]. On treatment of 10 and 11 with HBF4 . OEt(2), the cationic alkenylrhodium(III) derivatives [Rh(acac){(E)-CH=CHCy}(PCy(3))(2)]BF4 (12) and [Rh(acac)(CH=CH2)(PCy(3))(2)]BF4 (13) are obtained. Labeling experiments using DBF4 . OEt(2) illustrate that the deuterium is found at the beta-C carbon atom of the alkenyl ligand. Both 12 and [Rh(acac){(E)-CH=CDCy}(PCy(3))(2)]BF4 (12-d(1)) react with NEt(3) to regenerate 10. The structure of 12 was determined by X-ray analysis. The coordination geometry around the metal center can be rationalized as a square pyramid with the alkenyl group in the apical position.

  DOI：

  10.1021/om9601458
• 作为产物：
  描述：

  Rh((CH₃CO)2CH)(P(C₆H₁₁)3)(C₈H₁₄) 、 丙炔酸甲酯 以 正己烷 为溶剂， 以68%的产率得到Rh((CH3CO)2CH)(P(C6H11)3)(η(2)-HCCCO2CH3)
  参考文献：
  名称：

  Substitution and Oxidative Addition Reactions of the Monoolefin Complex Rh(acac)(cyclooctene)(PCy₃) Including the X-ray Structure Analyses of Rh(acac)(PCy₃)₂ and [Rh(acac){(E)-CHCHCy}(PCy₃)₂]BF₄

  摘要：

  The olefin complex Rh(acac)(cyclooctene)(PCy(3)) (2), which is formed from Rh(acac)(cyclooctene)(2) (1) PCy(3) in nearly quantitative yield, reacts with CO and alkynes RC=CR by ligand displacement to give Rh(acac)(CO)(PCy(3)) (3) and Rh(acac)(eta(2)-RC=CR)(PCy(3)) [R=CO(2)Me (4), Ph (5)], respectively. The bis(phosphine) compound Rh(acac)(PCy(3))(2) (6) cannot be prepared directly from 2 and excess PCy(3) but via Rh(acac)(eta(2)-HC=CCO(2)Me)(PCy(3)) (7) as intermediate. The X-ray crystal structure analysis of 6 reveals that the rhodium is coordinated in a distorted square-planar manner with O-Rh-O and P-Rh-P bond angles of 85.9(1) and 105.63(4)degrees. Compound 2 reacts with H-2 in the presence of PCy(3) to yield Rh(acac)H-2(PCy(3))(2) (8) and with HC=CR/PCy(3) to give Rh(acac)H(C=CR)(PCy(3))(2) [R=Ph (9), Cy (10), SiMe(3) (11)]. On treatment of 10 and 11 with HBF4 . OEt(2), the cationic alkenylrhodium(III) derivatives [Rh(acac){(E)-CH=CHCy}(PCy(3))(2)]BF4 (12) and [Rh(acac)(CH=CH2)(PCy(3))(2)]BF4 (13) are obtained. Labeling experiments using DBF4 . OEt(2) illustrate that the deuterium is found at the beta-C carbon atom of the alkenyl ligand. Both 12 and [Rh(acac){(E)-CH=CDCy}(PCy(3))(2)]BF4 (12-d(1)) react with NEt(3) to regenerate 10. The structure of 12 was determined by X-ray analysis. The coordination geometry around the metal center can be rationalized as a square pyramid with the alkenyl group in the apical position.

  DOI：

  10.1021/om9601458