[Cp(*)Rh(Me)(P(OMe)3)(anisaldehyde)]BAr'4 | 823202-82-0

• 英文名称: [Cp(*)Rh(Me)(P(OMe)3)(anisaldehyde)]BAr'4
• CAS: 823202-82-0
• 化学式: C₂₂H₃₅O₅PRh*C₃₂H₁₂BF₂₄
• 分子量: 1376.62
• InChiKey: LLFNUPXKABFXCQ-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：

  [Cp(*)Rh(Me)(P(OMe)3)(anisaldehyde)]BAr'4 、 4-甲氧基苯甲醛 以 not given 为溶剂， 生成 [Cp(*)Rh(P(OMe)33)(anisaldehyde)(4-CH3C6H4C(O))]BAr'4
  参考文献：
  名称：

  Aromatic and aldehyde carbon–hydrogen bond activation at cationic Rh(III) centers. Evaluation of electronic substituent effects on aldehyde binding and C–H oxidative addition

  摘要：

  Cationic rhodium methyl complexes, [Cp-*(PMe3)Rh(Me)(CH2Cl2)]BAr4' (1) and [Cp-*(P(OMe)(3))Rh(Me)(CH2Cl2)]BAr4' (3), react with benzene to yield the corresponding phenyl complexes, [Cp-*(PMe3)Rh(Ph)(CH2Cl2)]BAr4' (6) and [Cp-*(P(OMe)(3))Rh(Ph)(CH2Cl2)]BAr4' (7). First-order rate constants observed in 1.1 M benzene in CD2Cl2 at 25 degreesC are (2.1 +/- 0.2) x 10(-5) s(-1) and (1.9 +/- 0.2) x 10(-5) s(-1), respectively. Reactions of 1 and 3 with p-X-substituted benzaldehydes (X = -CF3, -CH3, and -OMe) initially produce the sigma-aldehyde adducts, [Cp-*(L)Rh(Me)(p-XC6H4CHO)]BAr4' (L = PMe3 (15), P(OMe)(3) (16)). Exchange of free with bound aldehyde occurs via a dissociative process and quantitative NMR rate measurements show that complexes of 1 exchange faster than those of 3 and that less basic aldehydes exchange faster than more basic aldehydes (p-CF3C6H4CHO > p-CH3C6H4CHO > p-CH3OC6H4CHO). The aldehyde adducts undergo C-H bond activation to produce initially methane plus acyl aldehyde adducts, [Cp-*(L)Rh(C(O)C6H4X)(p - XC6H4CHO)]BAr4' (L = PMe3 (17), P(OMe)(3) (18)). Rates of C-H activation are correlated with aldehyde exchange rates; activation barriers of weakly bound aldehydes are lower than more strongly bound aldehydes. In the case of L = PMe3, decarbonylation of the aldehyde adducts occurs cleanly to form aryl carbonyl complexes, [Cp-*(PMe3)Rh(C6H4X)(CO)]BAr4'. For L = P(OMe)(3), decarbonylation is a more complicated process; some intermediates and products have been identified by NMR spectroscopy. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2004.09.005
• 作为产物：
  描述：

  [Cp(*)Rh(Me)(P(OMe)3)ClCH2Cl]BAr'4 、 4-甲氧基苯甲醛 以 二氯甲烷-D2 为溶剂， 生成 [Cp(*)Rh(Me)(P(OMe)3)(anisaldehyde)]BAr'4
  参考文献：
  名称：

  Aromatic and aldehyde carbon–hydrogen bond activation at cationic Rh(III) centers. Evaluation of electronic substituent effects on aldehyde binding and C–H oxidative addition

  摘要：

  Cationic rhodium methyl complexes, [Cp-*(PMe3)Rh(Me)(CH2Cl2)]BAr4' (1) and [Cp-*(P(OMe)(3))Rh(Me)(CH2Cl2)]BAr4' (3), react with benzene to yield the corresponding phenyl complexes, [Cp-*(PMe3)Rh(Ph)(CH2Cl2)]BAr4' (6) and [Cp-*(P(OMe)(3))Rh(Ph)(CH2Cl2)]BAr4' (7). First-order rate constants observed in 1.1 M benzene in CD2Cl2 at 25 degreesC are (2.1 +/- 0.2) x 10(-5) s(-1) and (1.9 +/- 0.2) x 10(-5) s(-1), respectively. Reactions of 1 and 3 with p-X-substituted benzaldehydes (X = -CF3, -CH3, and -OMe) initially produce the sigma-aldehyde adducts, [Cp-*(L)Rh(Me)(p-XC6H4CHO)]BAr4' (L = PMe3 (15), P(OMe)(3) (16)). Exchange of free with bound aldehyde occurs via a dissociative process and quantitative NMR rate measurements show that complexes of 1 exchange faster than those of 3 and that less basic aldehydes exchange faster than more basic aldehydes (p-CF3C6H4CHO > p-CH3C6H4CHO > p-CH3OC6H4CHO). The aldehyde adducts undergo C-H bond activation to produce initially methane plus acyl aldehyde adducts, [Cp-*(L)Rh(C(O)C6H4X)(p - XC6H4CHO)]BAr4' (L = PMe3 (17), P(OMe)(3) (18)). Rates of C-H activation are correlated with aldehyde exchange rates; activation barriers of weakly bound aldehydes are lower than more strongly bound aldehydes. In the case of L = PMe3, decarbonylation of the aldehyde adducts occurs cleanly to form aryl carbonyl complexes, [Cp-*(PMe3)Rh(C6H4X)(CO)]BAr4'. For L = P(OMe)(3), decarbonylation is a more complicated process; some intermediates and products have been identified by NMR spectroscopy. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2004.09.005