[RhCl(phenylpyrazole)(η5-C5Me5)] | 1259203-29-6

• 英文名称: [RhCl(phenylpyrazole)(η5-C5Me5)]
• 英文别名: [2-(1H-pyrazol-1-yl)phenyl](pentamethylcyclopentadienyl)rhodium(III) chloride
• CAS: 1259203-29-6
• 化学式: C₁₉H₂₂ClN₂Rh
• 分子量: 416.756
• InChiKey: QKTSBWRFYYLKGF-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 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：

  [RhCl(phenylpyrazole)(η5-C5Me5)] 、 二苯基乙炔 以 甲醇 为溶剂， 以81%的产率得到1-[2-(1,2-diphenylethenyl)phenyl]pyrazole;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;rhodium(3+);chloride
  参考文献：
  名称：

  Alkyne insertion into cyclometallated pyrazole and imine complexes of iridium, rhodium and ruthenium; relevance to catalytic formation of carbo- and heterocycles

  摘要：

  环金属化配合物 [MCl(C⁁N)(环)]（HC⁁N = 2-苯基吡唑，M = Ir，Rh 环 = Cp*；M = Ru，环 = 对伞花烃）很容易与 RCCR 进行插入反应（ R = CO2Me, Ph) 得到单插入产物，铑配合物也与 PhCCH 区域特异性反应，得到类似的产物。环金属化亚胺配合物 [MCl(C^N)Cp*] (HC⁁N = PhCHNR, R = Ph, CH2CH2OMe, Me; M = Ir, Rh) 与 PhCCPh 的反应产物取决于取代基 R；当 R = CH2CH2OMe 时，观察到单插入，然而，对于 R = Me，初始插入产物不稳定，经历还原消除并损失有机片段，而对于 R = Ph，没有分离出含金属产物。与PhCCH一起，环金属化亚胺络合物可以得到单插入或双插入产物。讨论了串联 C-H 活化、炔插入机制催化合成碳环和杂环的影响。

  DOI：

  10.1039/c0dt00280a
• 作为产物：
  描述：

  dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 1-苯基吡唑 在 sodium acetate 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以84%的产率得到[RhCl(phenylpyrazole)(η5-C5Me5)]
  参考文献：
  名称：

  铑 (III) 催化的电氧化 C-C 烯基化

  摘要：

  电化学 CC 活化是通过方便的氧化铑 (III) 催化完成的。因此，氧化性 CC 烯基化证明在电的帮助下是可行的，避免使用有毒和/或昂贵的过渡金属氧化剂。螯合辅助的 CC 功能化在有机金属 CC 活化歧管内以广泛的范围和优异的化学和位置选择性进行。详细的机理研究为动力学相关的 CC 断裂提供了支持，并且明确定义的有机金属铑 (III) 配合物被确定为具有催化能力的中间体。电化学 CC 功能化不需要额外的电解质，可以在克规模上进行，并提供对密集的 1,2,3-取代芳烃的位置选择性访问，这些芳烃不能通过 CH 活化。

  DOI：

  10.1021/jacs.8b13692

文献信息

• Rh(III)-Catalyzed Aryl and Alkenyl C–H Bond Addition to Diverse Nitroalkenes
  作者：Tyler J. Potter、David N. Kamber、Brandon Q. Mercado、Jonathan A. Ellman

  DOI：10.1021/acscatal.6b03217

  日期：2017.1.6

  The transition-metal-catalyzed C–H bond addition to nitroalkenes has been developed. Very broad nitroalkene scope was observed for this Rh(III)-catalyzed method, including for aliphatic, aromatic, and β,β-disubstituted derivatives. Additionally, various directing groups and both aromatic and alkenyl C–H bonds were effective in this transformation. Representative nitroalkane products were converted

  已经开发了过渡金属催化的C–H键加到硝基烯烃中的方法。对于此Rh（III）催化方法，观察到非常广泛的硝基烯烃范围，包括脂肪族，芳香族和β，β-二取代衍生物。此外，在该转化过程中，各种导向基团以及芳族和烯基CH键均有效。代表性的硝基烷烃产物通过铁介导的还原和原位环化反应，一步一步即可高产率地转化为二氢异喹诺酮和二氢吡啶酮。此外，通过对硝基化合物中间体的X射线结构表征，初步获得了对映体选择性Rh（III）催化的C–H键向硝基烯烃的加成反应。
• Experimental and DFT Studies Explain Solvent Control of C–H Activation and Product Selectivity in the Rh(III)-Catalyzed Formation of Neutral and Cationic Heterocycles
  作者：David L. Davies、Charles E. Ellul、Stuart A. Macgregor、Claire L. McMullin、Kuldip Singh

  DOI：10.1021/jacs.5b04858

  日期：2015.8.5

  A range of novel heterocyclic cations have been synthesized by the Rh(III)-catalyzed oxidative C-N and C-C coupling of 1-phenylpyrazole, 2-phenylpyridine, and 2-vinyl-pyridine with alkynes (4-octyne and diphenylacetylene). The reactions proceed via initial C-H activation, alkyne insertion, and reductive coupling, and all three of these steps are sensitive to the substrates involved and the reaction conditions. Density functional theory (DFT) calculations show that C-H activation can proceed via a heteroatom-directed process that involves displacement of acetate by the neutral substrate to form charged intermediates. This step (which leads to cationic C-N coupled products) is therefore favored by more polar solvents. An alternative non-directed C-H activation is also possible that does not involve acetate displacement and so becomes favored in low polarity solvents, leading to C-C coupled products. Alkyne insertion is generally more favorable for diphenylacetylene over 4-octyne, but the reverse is true of the reductive coupling step. The diphenylacetylene moiety can also stabilize unsaturated seven-membered rhodacycle intermediates through extra interaction with one of the Ph substituents. With 1-phenylpyrazole this effect is sufficient to suppress the final C-N reductive coupling. A comparison of a series of seven-membered rhodacycles indicates the barrier to coupling is highly sensitive to the two groups involved and follows the trend C-N+ > C-N > C-C (i.e., involving the formation of cationic C-N, neutral C-N, and neutral C-C coupled products, respectively).