Octahedral Iron‐Acyl‐Nitrenoid Intermediates in Sulphur −Nitrogen Coupling and Hydrogen Atom Transfer Reactions.

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, octahedral iron complexes can be air‐stable alternatives forming the iron‐nitrenoid species. Here, a novel octahedral non‐heme iron‐acyl‐nitrenoid complex is presented. Its reactivity was studied using a flow chemistry setup with online mass spectrometry detection, which allows qualitative reaction kinetics evaluation and the detection of the intermediates. The iron‐nitrenoid complex reacts with thiophenol by H‐Atom transfer, followed by a rebound to form a new N−S bond. The rebound intermediate could be detected and distinguished from the product complex. The reaction of the iron‐acyl‐nitrenoid complex with hydrocarbons results in the activation of the C−H bond via hydrogen‐atom transfer with no subsequent rebound process. [ABSTRACT FROM AUTHOR]