Tracking Reaction Pathways by a Modular Flow Reactor Coupled to Electrospray Ionization Mass Spectrometry

Reaction monitoring by electrospray ionization mass spectrometry (ESI-MS) is a popular method for investigation of reaction mechanisms. Here, we present new approach based on coupling between modular capillary flow reactor and ESI-MS. The allows sequential adding the reactants. We demonstrate oxidation Ph2S ArIO catalyzed [(TPA)Fe(TfO)2] (ArIO=2-(tBuSO2)C6H4IO, TPA=tris(2-pyridylmethyl)amine, TfO?=triflate). In steps, could follow formation reactive iron(IV)oxo complexes, then oxygen transfer from to sulfide, finally reoxidation iron complexes. also kinetic experiments changing relative concentrations analyze in detail various [(TPA)FeIVO(X)]2+/+ complexes (X=MeCN, ArI, ArIO, TfO?) compare their reactivity with Ph2S. [(TPA)FeIVO(MeCN)]2+ complex most atom whilst [(TPA)FeIVO(ArIO)]2+ prevails solution under catalytic conditions.