title: Carbonylation of alkyl halides with [Fe(CO)3(NO)]-: in silico identification of a common intermediate.
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.
authors.affiliation: Institut für Organische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany.
authors.forename: Johannes E M N
authors.initials: JE
authors.lastname: Klein
authors.forename: Burkhard
authors.initials: B
authors.lastname: Miehlich
authors.forename: Johannes
authors.initials: J
authors.lastname: Kästner
authors.forename: Bernd
authors.initials: B
authors.lastname: Plietker
mesh_terms: D000215:Acylation; D000478:Alkylation; D003198:Computer Simulation; D005296:Ferrous Compounds / Q000737:chemistry*; D007536:Isomerism; D008958:Models, Molecular; D011789:Quantum Theory
chemical_list: D005296:Ferrous Compounds