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)(P) precursor followed by the diazoalkane coordination and the N extrusion. The free energy of activation is predicted to be 18.5 and 28.2 kcal/mol for the PF and PPh containing systems, respectively. Thus, in the presence of less basic P-donor ligands with stronger π-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)(phosphine)(-CHN) adduct reveals a π-donor-π-acceptor type of coordination.
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| http://dx.doi.org/10.3390/molecules25245860 | DOI Listing |
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