An innovative approach aimed at disclosing the mechanism of chemical reactions occurring in solution on the millisecond time scale is presented. Time-resolved energy dispersive X-ray absorption and UV/vis spectroscopies with millisecond resolution are used simultaneously to directly follow the evolution of both the oxidation state and the local structure of the metal center in an iron complex. Two redox reactions are studied, the former involving the transformation of FeII into two subsequent FeIII species and the latter involving the more complex FeII−FeIII−FeIV−FeIII sequence. The structural modifications occurring around the iron center are correlated to the reaction mechanisms. This combined approach has the potential to provide unique insights into reaction mechanisms in the liquid phase and represents a new powerful tool to characterize short-lived intermediates that are silent to common spectroscopic techniques.

Following a chemical reaction on the millisecond time scale by simultaneous X-ray and UV/Vis spectroscopy / Olivo, Giorgio; Barbieri, Alessia; Dantignana, Valeria; Sessa, Francesco; Migliorati, Valentina; Monte, Manuel; Pascarelli, Sakura; Narayanan, Theyencheri; Lanzalunga, Osvaldo; DI STEFANO, Stefano; D'Angelo, Paola. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - STAMPA. - 8:13(2017), pp. 2958-2963. [10.1021/acs.jpclett.7b01133]

Following a chemical reaction on the millisecond time scale by simultaneous X-ray and UV/Vis spectroscopy

OLIVO, GIORGIO;BARBIERI, ALESSIA;SESSA, FRANCESCO;MIGLIORATI, VALENTINA;LANZALUNGA, Osvaldo
;
DI STEFANO, Stefano
;
D'ANGELO, Paola
2017

Abstract

An innovative approach aimed at disclosing the mechanism of chemical reactions occurring in solution on the millisecond time scale is presented. Time-resolved energy dispersive X-ray absorption and UV/vis spectroscopies with millisecond resolution are used simultaneously to directly follow the evolution of both the oxidation state and the local structure of the metal center in an iron complex. Two redox reactions are studied, the former involving the transformation of FeII into two subsequent FeIII species and the latter involving the more complex FeII−FeIII−FeIV−FeIII sequence. The structural modifications occurring around the iron center are correlated to the reaction mechanisms. This combined approach has the potential to provide unique insights into reaction mechanisms in the liquid phase and represents a new powerful tool to characterize short-lived intermediates that are silent to common spectroscopic techniques.
2017
nonheme iron catalysts; stereospecific alkane hydroxylation; complexes
01 Pubblicazione su rivista::01a Articolo in rivista
Following a chemical reaction on the millisecond time scale by simultaneous X-ray and UV/Vis spectroscopy / Olivo, Giorgio; Barbieri, Alessia; Dantignana, Valeria; Sessa, Francesco; Migliorati, Valentina; Monte, Manuel; Pascarelli, Sakura; Narayanan, Theyencheri; Lanzalunga, Osvaldo; DI STEFANO, Stefano; D'Angelo, Paola. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - STAMPA. - 8:13(2017), pp. 2958-2963. [10.1021/acs.jpclett.7b01133]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/991259
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