{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,24]],"date-time":"2026-06-24T04:21:49Z","timestamp":1782274909113,"version":"3.54.5"},"reference-count":41,"publisher":"MDPI AG","issue":"24","license":[{"start":{"date-parts":[[2020,12,11]],"date-time":"2020-12-11T00:00:00Z","timestamp":1607644800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The mechanism of the carbonylation of diazomethane in the presence of iron\u2013carbonyl\u2013phosphine 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 \u03c0-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\u2013NOCV) calculations, diazomethane in the Fe(CO)3(phosphine)(\u03b71-CH2N2) adduct reveals a \u03c0-donor\u2013\u03c0-acceptor type of coordination.<\/jats:p>","DOI":"10.3390\/molecules25245860","type":"journal-article","created":{"date-parts":[[2020,12,14]],"date-time":"2020-12-14T00:45:36Z","timestamp":1607906736000},"page":"5860","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["DFT Study on the Mechanism of Iron-Catalyzed Diazocarbonylation"],"prefix":"10.3390","volume":"25","author":[{"given":"T\u00edmea R.","family":"K\u00e9gl","sequence":"first","affiliation":[{"name":"Department of Inorganic Chemistry and MTA-PTE Research Group for Selective Chemical Syntheses, University of P\u00e9cs, H-7624 P\u00e9cs, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0231-4148","authenticated-orcid":false,"given":"L\u00e1szl\u00f3","family":"Koll\u00e1r","sequence":"additional","affiliation":[{"name":"Department of Inorganic Chemistry and MTA-PTE Research Group for Selective Chemical Syntheses, University of P\u00e9cs, H-7624 P\u00e9cs, Hungary"},{"name":"Department of Inorganic Chemistry and J\u00e1nos Szent\u00e1gothai Research Centre, University of P\u00e9cs, H-7624 P\u00e9cs, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4642-1703","authenticated-orcid":false,"given":"Tam\u00e1s","family":"K\u00e9gl","sequence":"additional","affiliation":[{"name":"Department of Inorganic Chemistry and MTA-PTE Research Group for Selective Chemical Syntheses, University of P\u00e9cs, H-7624 P\u00e9cs, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2020,12,11]]},"reference":[{"key":"ref_1","unstructured":"Tidwell, T.T. 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