American Chemical Society
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Probing the Carbon–Hydrogen Activation of Alkanes Following Photolysis of Tp′Rh(CNR)(carbodiimide): A Computational and Time-Resolved Infrared Spectroscopic Study

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journal contribution
posted on 2017-12-31, 00:00 authored by Jia Guan, Alisdair Wriglesworth, Xue Zhong Sun, Edward N. Brothers, Snežana D. Zarić, Meagan E. Evans, William D. Jones, Michael Towrie, Michael B. Hall, Michael W. George
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 υ­(CNR) and υ­(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: κ31-alkane complex (1); κ22-alkane complex (2); and κ3-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) and 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 κ22-alkane Tp′ complexes stabilizes the d8 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 κ2-Tp′Rh­(CNR)­(cycloalkane) species and results in the C–H activation without the assistance of the rechelation.