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Frisch, M et al. Gaussian 98, revision A.11.4; Gaussian, Inc: Pittsburgh, PA, 2001. Calculations used the BP86 functional. Pd was described using the Stuttgart RECPs and the associated basis sets; 6-31G** basis sets were used for C, N, O, and H atoms. Quoted energies include a correction for zero-point energies. See Supporting Information for full details.
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26444473392
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note
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While the C-H bond activation step is rate-determining in chloroform, the kinetics are very different in acetic acid. Our calculations should, therefore, only be taken to represent the situation in low polarity media.
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Full details, including all stationary points, are illustrated in Figures S1 and S2 in the Supporting Information.
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26444484083
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4-X) species were 15.0 (X = Cl), 14.2 (X = H), and 13.2 (X = Me).
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nPr indicate that alkyl-C-H activation proceeds with a barrier of only 20 kcal/mol.
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