DFT Study on the Mechanism of Iron-Catalyzed Diazocarbonylation

Kégl, Tímea R. and Kollár, László and Kégl, Tamás (2020) DFT Study on the Mechanism of Iron-Catalyzed Diazocarbonylation. MOLECULES, 25 (24). pp. 1-13. ISSN 1420-3049

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Abstract

The mechanism of the carbonylation of diazomethane in the presence of iron–carbonyl–phosphine catalysts has been investigated by means of DFT calculations at the M06/def-TZVP//B97D3/def2-TZVP level of theory, in combination with the SMD solvation method. The reaction rate is determined by the formation of the coordinatively unsaturated doublet-state Fe(CO)3(P) precursor followed by the diazoalkane coordination and the N2 extrusion. The free energy of activation is predicted to be 18.5 and 28.2 kcal/mol for the PF3 and PPh3 containing systems, respectively. Thus, in the presence of less basic P-donor ligands with stronger p-acceptor properties, a significant increase in the reaction rate can be expected. According to energy decomposition analysis combined with natural orbitals of chemical valence (EDA–NOCV) calculations, diazomethane in the Fe(CO)3(phosphine)(h1-CH2N2) adduct reveals a p-donor–p-acceptor type of coordination.

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