Octahedral Iron-Acyl-Nitrenoid Intermediates in Sulphur –Nitrogen Coupling and Hydrogen Atom Transfer Reactions

April 4, 2023

Title

Octahedral Iron-Acyl-Nitrenoid Intermediates in Sulphur –Nitrogen Coupling and Hydrogen Atom Transfer Reactions

Author

Rodríguez, Monica, Aleksandr Y. Pereverzev, and Jana Roithová

Year

2023

Journal

ChemCatChem

Abstract

Iron-nitrenoid complexes can activate C?H bonds and, thus, potentially directly transform C?H into C?N bonds. Low-coordination complexes are the main reported systems; however,octahedralironcomplexescanbeair-stablealternativesformingtheiron-nitrenoidspecies.Here,wepresentanoveloctahedralnon-hemeiron-acyl-nitrenoidcomplex.Itsreactivitywasstudiedusingaflowchemistrysetupwithonlinemassspectrometrydetection,whichallowsqualitativereactionkineticsevaluationandthedetectionoftheintermediates.Theiron-nitrenoidcomplexreactswiththiophenolbyH-Atomtransfer,followedbyareboundtoformanewN?Sbond.Thereboundintermediatecouldbedetectedanddistinguishedfromtheproductcomplex.Thereactionoftheiron-acyl-nitrenoidcomplexwithhydrocarbonsresultsintheactivationoftheC?Hbondviahydrogen-atomtransferwithnosubsequentreboundprocess

Instrument

V-630

Keywords

H atom transfer,iron imido,reaction intermediates,reaction mechanism