This work utilizes density functional theory and the energetic span model to determine steps constituting the catalytic cycle and turnover frequencies, respectively, for C(sp)-Cl activation and dechlorination by model Rh(I) complexes containing POP-Pincer ligands with the aid of Na salts. The steps in the catalytic cycle with NaHCO as the hydrogen carrier are (i) rotation of the Rh-Cl bond out of the ligand plane, (ii) metal insertion into the C-Cl bond, (iii) formate binding and removal of one Cl as NaCl, (iv) formation and removal of CO from formate-bound Rh, and (v) hydrogenation of the alkyl bound to Rh to form an alkane, followed by Rh-Cl rotation to restore the catalyst resting state. We find that the the turnover-determining states and TOFs for monochloropropane (MCP) dechlorination depend strongly on the hydrogen carrier, with significantly higher TOF for NaH than NaHCO. Therefore, NaH may be a promising salt for alkylchloride dechlorination with Rh(I) complexes.
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