Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp'Rh(CNR)(carbodiimide): A Computational and Time Resolved Infrared Spectroscopic Study
Sun, Xue Zhong
Brothers, Edward N.
Zarić, Snežana D.
Evans, Meagan E.
Jones, William D.
Hall, Michael B.
George, Michael W.
Article (Accepted Version)
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Carbon-hydrogen bond activation of alkanes by Tp'Rh(CNR) (Tp' = Tp = trispyrazolylborate or Tp* = tris(3,5- dimethylpyrazolyl)borate) were followed by time-resolved infrared spectroscopy (TRIR) in the upsilon(CNR) and upsilon(B-H) spectral regions on Tp*Rh(CNCH2CMe3), and their reaction mechanisms were modeled by density functional theory (DFT) on TpRh(CNMe). The major intermediate species were: kappa(3)-eta(1)-alkane complex (1); kappa(2)-kappa(2)-alkane complex (2); and kappa(3)-alkyl hydride (3). Calculations predict that the barrier between 1 and 2 arises from a triplet-singlet crossing and intermediate 2 proceeds over the rate-determining C-H activation barrier to give the final product 3. The activation lifetimes measured for the Tp*Rh(CNR) and Tp*Rh(CO) fragments with n-heptane and four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) increase with alkanes size and show a dramatic increase between C6H12 and C7H14. A similar step-like behavior was observed previously with CpRh(CO) a...nd Cp*Rh(CO) fragments and is attributed to the wider difference in C-H bonds that appear at C7H14. However, Tp'Rh(CNR) and Tp'Rh(CO) fragments have much longer absolute lifetimes compared to those of CpRh(CO) and Cp*Rh(CO) fragments, because the reduced electron density in dechelated kappa(2)-eta(2)-alkane Tp' complexes stabilizes the d(8) Rh(I) in a square-planar geometry and weakens the metal's ability for oxidative addition of the C-H bond. Further, the Tp'Rh(CNR) fragment has significantly slower rates of C-H activation in comparison to the Tp'Rh(CO) fragment for the larger cycloalkanes, because the steric bulk of the neopentyl isocyanide ligand hinders the rechelation in kappa(2)-Tp'Rh(CNR)(cycloalkane) species and results in the C-H activation without the assistance of the rechelation.
Source:Journal of the American Chemical Society, 2018, 140, 5, 1842-1854
- Amer Chemical Soc, Washington
- Welch Foundation [A-0648]
- University of Nottingham Ningbo China
- Qatar National Research Fund (NPRP) [7-297-1-051]
- EPSRC [EP/I01974X]
- This is the peer-reviewed version of the following article: Guan, J.; Wriglesworth, A.; Sun, X. Z.; Brothers, E. N.; Zarić, S. D.; Evans, M. E.; Jones, W. D.; Towrie, M.; Hall, M. B.; George, M. W. Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp′Rh(CNR)(Carbodiimide): A Computational and Time-Resolved Infrared Spectroscopic Study. Journal of the American Chemical Society 2018, 140 (5), 1842–1854. https://doi.org/10.1021/jacs.7b12152
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/2942