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Published on: February 20, 2020
Carbonylation of alkyl halides with [Fe(CO)3(NO)]-: in silico identification of a common intermediate
Johannes E M N Klein1, Burkhard Miehlich, Johannes Kästner
1Institut für Organische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany.
Abstract:
The mechanism of carbonylation of alkyl halides using [Fe(CO)3(NO)](-) has been studied using density functional theory (DFT). Our results suggest an SN2 mechanism for the alkylation event followed by a well-defined oxidative addition and alkyl migration. An experimentally elusive common intermediate [Fe(CO)2NO(Ac)] has been identified in two isomers and reacted in silico with a number of ligands (CO, PH3 and PPh3) to give the corresponding iron acyl complexes. Pathways between the two isomers, including direct involvement of a solvent molecule (THF) or iodide, have been elucidated.
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Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
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