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The Mechanism of a C-H Bond Activation Reaction in Room-Temperature Alkane Solution
Abstract
Chemical reactions that break alkane carbon-hydrogen (C–H) bonds are normally carried out under conditions of high temperature and pressure because these bonds are extremely strong (∼100 kilocalories per mole), but certain metal complexes can activate C–H bonds in alkane solution under the mild conditions of room temperature and pressure. Time-resolved infrared experiments probing the initial femtosecond dynamics through the nano- and microsecond kinetics to the final stable products have been used to generate a detailed picture of the C–H activation reaction. Structures of all of the intermediates involved in the reaction of Tp*Rh(CO) 2 (Tp* = HB–Pz 3 *, Pz* = 3,5-dimethylpyrazolyl) in alkane solution have been identified and assigned, and energy barriers for each reaction step from solvation to formation of the final alkyl hydride product have been estimated from transient lifetimes.
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Citations
Cited by
Understanding and exploiting C–H bond activation
Labinger, J. A., & Bercaw, J. E. (2002) · Nature · doi:10.1038/417507a · Cited by 2,768
Solar-Energy-Mediated Methane Conversion
Song, H., Meng, X., Wang, Z.-J., Liu, H., & Ye, J. (2019) · Joule · doi:10.1016/j.joule.2019.06.023 · Cited by 478
Dai, Y., Poidevin, C., Ochoa‐Hernández, C., Auer, A. A., & Tüysüz, H. (2020) · Angewandte Chemie International Edition · doi:10.1002/anie.201915034 · Cited by 269
Kunnus, K., Josefsson, I., Rajkovic, I., Schreck, S., Quevedo, W., Beye, M., Weniger, C., Grübel, S., Scholz, M., Nordlund, D., et al. (2016) · Structural Dynamics · doi:10.1063/1.4941602 · Cited by 60
Metadata
- Authors
- Bromberg, S. E., Yang, H., Asplund, M. C., Lian, T., McNamara, B. K., Kotz, K. T., Yeston, J. S., Wilkens, M., Frei, H., Bergman, R. G., & Harris, C. B.
- Venue
- Science
- Published
- 1997-10-10
- Volume
- 278
- Issue
- 5336
- Pages
- 260-263
- ISSN
- 0036-8075 (ISSN-L)
- 1095-9203
- OpenAlex
- W2165809456
- Cited by
- 269
- References
- 0
- FWCI
- 16.39
- Type
- journal article
- Language
- en
- Open access
- closed
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- Bromberg, S. E., Yang, H., Asplund, M. C., Lian, T., McNamara, B. K., Kotz, K. T., Yeston, J. S., Wilkens, M., Frei, H., Bergman, R. G., & Harris, C. B. (1997). The Mechanism of a C-H Bond Activation Reaction in Room-Temperature Alkane Solution. Science. https://doi.org/10.1126/science.278.5336.260
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