Corrigendum to: Formation Mechanism of the First Carbon-Carbon Bond and the First Olefin in the Methanol Conversion into Hydrocarbons (Angewandte Chemie International Edition, (2016), 55, 19, (5723-5726), 10.1002/anie.201511678)

In this Communication, an erroneous use of a literature reported reaction rate as a rate constant was made in the rate calculation in Supporting Information S9: “A semi-quantitative estimation of the carbonylation rate is made based on reported kinetic data from literature. A rate constant of 6.8 mol (g atom Al)⁻¹ h⁻¹ was applied for the reaction on HZSM-5 at 450 °C, according to literature (Fig. 1 Angew. Chem. Int. Ed. 2006, 45, 1617-1620). Applying a reaction order of 1 for CO and 0 for dimethyl ether, and an H-ZSM-5(Si/Al 90) loading of 1 g, acetyl species (HOAc and MeOAc) formation rate of 560 μmol/min under 1 mbar CO or 5.6 μmol/min under 0.01 mbar CO was obtained.” A new estimation of the carbonylation rate was made by the authors based on their experimental data. Thus, the statement must be corrected to “A semi-quantitative estimation of the carbonylation rate is made based on our experimental results over H-ZSM-5(Si/Al 90). A carbon-based reaction rate constant of 140 mmol (g cat)⁻¹ h⁻¹ (bar CO)⁻¹ at 450 °C was obtained from our DME carbonylation experiment. Applying a reaction order of 1 for CO and 0 for dimethyl ether, and an H-ZSM-5 loading of 1 g, acetyl species (HOAc and MeOAc) formation rate is calculated to be 140 μmol h⁻¹ (2.3 μmol min⁻¹) under 1 mbar CO.” At 450 °C, this catalyst showed an initial period of ca. 1.5 h (g cat)⁻¹ (mol MeOH)⁻¹ before the detection of olefins, and ca. 0.4 % yield of methane from which CO is estimated to be ca. 0.7 mbar. This leads to a yield of 150 ppm of acetyl species during this initial period, which was demonstrated, in the DME carbonylation experiment, to be sufficient to trigger olefin formation at even 300 °C. Thus, the corrected calculation does not change the conclusion on the slow rate for the carbonylation process and the sufficiency of the accumulated acetyl products to trigger the formation of hydrocarbon pool. The authors acknowledge the helpful comments from Prof. Aditya Bhan, University of Minnesota.