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首页> 外文期刊>Proceedings of the National Academy of Sciences of the United States of America >Understanding the factors affecting the activation of alkane by Cp'Rh(CO)2 (Cp' = Cp or Cp*)
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Understanding the factors affecting the activation of alkane by Cp'Rh(CO)2 (Cp' = Cp or Cp*)

机译：了解影响Cp'Rh（CO）2活化烷烃的因素（Cp'= Cp或Cp *）

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摘要

Fast time-resolved infrared spectroscopic measurements have allowed precise determination of the rates of activation of alkanes by Cp'Rh(CO) (Cp' = η5-C5H5 or η5-C5Me5). We have monitored the kinetics of C-H activation in solution at room temperature and determined how the change in rate of oxidative cleavage varies from methane to decane. The lifetime of CpRh(CO)(alkane) shows a nearly linear behavior with respect to the length of the alkane chain, whereas the related Cp*Rh(CO)(alkane) has clear oscillatory behavior upon changing the alkane. Coupled cluster and density functional theory calculations on these complexes, transition states, and intermediates provide the insight into the mechanism and barriers in order to develop a kinetic simulation of the experimental results. The observed behavior is a subtle interplay between the rates of activation and migration. Unexpectedly, the calculations predict that the most rapid process in these Cp'Rh (CO)(alkane) systems is the 1,3-migration along the alkane chain. The linear behavior in the observed lifetime of CpRh(CO)(alkane) results from a mechanism in which the next most rapid process is the activation of primary C-H bonds (-CH3 groups), while the third key step in this system is 1,2-migration with a slightly slower rate. The oscillatory behavior in the lifetime of Cp*Rh(CO)(alkane) with respect to the alkane's chain length follows from subtle interplay between more rapid migrations and less rapid primary C-H activation, with respect to CpRh(CO)(alkane), especially when the CH3 group is near a gauche turn. This interplay results in the activation being controlled by the percentage of alkane conformers.
机译：快速的时间分辨红外光谱测量可以精确测定Cp'Rh（CO）（Cp'=η5-C5H5或η5-C5Me5）烷烃的活化速率。我们已经监测了室温下溶液中C-H活化的动力学，并确定了氧化裂解率的变化从甲烷到癸烷如何变化。 CpRh（CO）（烷烃）的寿命相对于烷烃链的长度表现出近乎线性的行为，而相关的Cp * Rh（CO）（烷烃）在改变烷烃时具有明显的振荡行为。在这些配合物，过渡态和中间体上进行的聚类和密度泛函理论计算，为深入研究机理和障碍提供了见识，从而可以对实验结果进行动力学模拟。观察到的行为是激活和迁移速率之间的微妙相互作用。出乎意料的是，计算预测这些Cp'Rh（CO）（烷烃）系统中最快速的过程是沿烷烃链的1,3-迁移。在观察到的CpRh（CO）（烷烃）寿命中的线性行为是由以下机制引起的：在该机制中，下一个最快速的过程是伯CH键（-CH3基团）的激活，而该系统的第三个关键步骤是： 2迁移速度稍慢。 Cp * Rh（CO）（烷烃）的寿命中相对于烷烃链长的振荡行为是由于相对于CpRh（CO）（烷烃），迁移速度更快而初级CH活化较慢，这之间存在微妙的相互作用。当CH3组靠近薄纱转弯时。这种相互作用导致活化受到烷烃构象异构体百分比的控制。

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  • 作者

    Michael W. George; Michael B. Hall; Omar S. Jina; Peter Portius; Xue-Zhong Sun; Michael Towrie; Hong Wu; Xinzheng Yang; Snezana D. Zaric;

  • 作者单位

    School of Chemistry, University of Nottingham, University Park NG7 2RD, United Kingdom;

    Department of Chemistry, Texas ASM University,College Station, TX 77843-3255;

    School of Chemistry, University of Nottingham, University Park NG7 2RD, United Kingdom;

    School of Chemistry, University of Nottingham, University Park NG7 2RD, United Kingdom;

    School of Chemistry, University of Nottingham, University Park NG7 2RD, United Kingdom;

    Central Laser Facility, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot OX11 0QX, United Kingdom;

    Department of Chemistry, Texas ASM University,College Station, TX 77843-3255;

    Department of Chemistry, Texas ASM University,College Station, TX 77843-3255;

    Department of Chemistry, University of Belgrade, Studentski Trg 16, P.O. Box 158,11001 Belgrade, Serbia;

  • 收录信息 美国《科学引文索引》(SCI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

    organometallic; photochemistry; computation; transition metal; sigma complex;

    机译：有机金属光化学计算过渡金属;sigma复合体;

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