(η5-pentamethylcyclopentadienyl)rhodium(III)Cl2(trimethylphosphite) | 172162-90-2

• 分子结构分类: 有机化合物 - 有机卤素化合物
• 英文名称: (η5-pentamethylcyclopentadienyl)rhodium(III)Cl2(trimethylphosphite)
• 英文别名: [Cp(*)Rh(P(OMe)3)Cl2；dichlororhodium(1+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene;trimethyl phosphite
• CAS: 172162-90-2
• 化学式: C₁₃H₂₄Cl₂O₃PRh
• 分子量: 433.117
• InChiKey: ZXDLPIOSVXXJDT-UHFFFAOYSA-L

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：
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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：

  (η5-pentamethylcyclopentadienyl)rhodium(III)Cl2(trimethylphosphite) 、 甲基锂 以 四氢呋喃 、 乙醚 为溶剂， 以50%的产率得到[Cp(*)Rh(Me)(P(OMe)3)Cl]
  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：

  氘代氯仿 、 以 氘代氯仿 为溶剂， 生成 (η5-pentamethylcyclopentadienyl)rhodium(III)Cl2(trimethylphosphite)
  参考文献：
  名称：

  合成，合成和本征合成环戊二烯基草酸酯-铑

  摘要：

  二聚体铑络合物[Cp x RhCl 2 ] 2（Cp x = C 5 Me 5，C 5  t Bu 2 H 3）与草酸银Ag 2 C 2 O 4的反应生成具有化学式[Cp]的聚合物。x Rh（C 2 O 4）] n高收率。这些化合物与路易斯碱L [L = DMSO，P（OMe）3，PPh 3，P（C 8 H 17）3在解聚反应后生成Cp x Rh（C 2 O 4）L类型的加成产物。这些化合物的溶解度取决于配体L。Cp * Rh（C 2 O 4）P（OMe）3仅可溶于极性有机溶剂，而Cp * Rh（C 2 O 4）P（C 8 H 17）3可以溶于非极性溶剂，如烷烃。所有这些化合物均耐空气和湿气。通过X射线分析已经解决了Cp * Rh（C 2 O 4）P（OMe）3的结构。Cp * Rh（C 2 O 4）的紫外线照射CHX 3（X = Cl，Br）中的）L（L = P（OMe）3，PPh 3）导致CO

  DOI：

  10.1016/s0022-328x(97)00725-0

文献信息

• One-pot syntheses of alkenyl-phosphonio complexes of ruthenium(II), rhodium(III) and iridium(III) bearing p-cymene or pentamethylcyclopentadienyl groups
  作者：Kenichi Ogata、Jyoji Seta、Yasuhiro Yamamoto、Katsuaki Kuge、Kazuyuki Tatsumi

  DOI：10.1016/j.ica.2007.03.053

  日期：2007.7

  and PPh 3 were carried out in the presence of KPF 6 , generating the corresponding alkenyl-phosphonio complexes, [( p -cymene)RuCl(PPh 3 )CH CR(PPh 3 )}](PF 6 ) ( 2a : R = Ph; 2b : R = p -tolyl) or [Cp ∗ MCl(PPh 3 )CH CPh(PPh 3 )}](PF 6 ) ( 5 : M = Rh; 6 : M = Ir). Similar reactions of complexes [Cp ∗ RhCl 2 (L 1 )] ( 3a : L 1 = PPh 3 ; 3c : L 1 = P(OMe) 3 ) with L 2 (L 2 = PPh 3 , PMePh 2 , P(OMe)

  [（p-Cymene）RuCl 2（PPh 3）]（1）或[CP ∗ MCl 2（PPh 3）]（CP ∗ = C 5 Me 5）（3a：M = Rh; 4a：M =在KPF 6的存在下，用1-炔烃和Ir（PPh 3）进行Ir）反应，生成相应的烯基-膦酰基络合物[[（p-Cymene）RuCl（PPh 3）CH CR（PPh 3）}]（PF 6） ）（2a：R = Ph; 2b：R = p-甲苯基）或[CP ∗ MCl（PPh 3）CH CPh（PPh 3）}]（PF 6）（5：M = Rh; 6：M = Ir ）。络合物[CP ∗ RhCl 2（L 1）]（3a：L 1 = PPh 3； 3c：L 1 = P（OMe）3）与L 2（L 2 = PPh 3，PMePh 2，P（OMe） ）3）给出[CP ∗ RhCl（L 1）（L 2）]（PF 6）（7bb：L 1 = L 2 = PMePh