Carbonylation of alkyl halides with [Fe(CO)3(NO)]−: In silico identification of a common intermediate

Johannes E.M.N. Klein; Burkhard Miehlich; Johannes Kästner; Bernd Plietker

doi:10.1039/c3dt50344e

Carbonylation of alkyl halides with [Fe(CO)₃(NO)]⁻: In silico identification of a common intermediate

Johannes E.M.N. Klein, Burkhard Miehlich, Johannes Kästner, Bernd Plietker

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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 S_N2 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.

Original language	English (US)
Pages (from-to)	7519-7525
Number of pages	7
Journal	Journal of the Chemical Society. Dalton Transactions
Volume	42
Issue number	21
DOIs	https://doi.org/10.1039/c3dt50344e
State	Published - Apr 15 2013
Externally published	Yes

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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.",

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T1 - Carbonylation of alkyl halides with [Fe(CO)3(NO)]−

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AU - Klein, Johannes E.M.N.

AU - Miehlich, Burkhard

AU - Kästner, Johannes

AU - Plietker, Bernd

PY - 2013/4/15

Y1 - 2013/4/15

N2 - 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.

AB - 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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JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

IS - 21

ER -

Carbonylation of alkyl halides with [Fe(CO)₃(NO)]⁻: In silico identification of a common intermediate

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