ESR study of paramagnetic iron carbonyl hydrides

Revisiting the polytopal rearrangements in penta-coordinate d7-metallocomplexes: modified Berry pseudorotation, octahedral switch, and butterfly isomerization

“…HFe˙(CO) 4 was first observed by Krusic et al in the mid-1980s using electron paramagnetic resonance (EPR) spectroscopy. 47 – 49 Nagorski and Mirbach proposed to utilize this radical as a precursor for the coordinatively unsaturated catalyst HFe˙(CO) 3 in the hydrogenation of 1-octane. 50 Our work was motivated by the observation of several elementary reactions involving polytopal rearrangements during a study of radical pathways in the photochemical and thermal hydrogenation of ethylene by Fe(CO) 5 -derived catalysts.…”

Einblicke in den Mechanismus der photokatalytischen Wasserreduktion durch DFT‐gestützte In‐situ‐EPR/Raman‐Spektroskopie

“…0385) zugeordnet werden. [13,14] 8 ] 2À (DMTED = N,N'-Dimethyltriethylendiamin) bei 178 cm À1 überein, der von Onaka und Shriver vermessen wurde. [15] Unter Bestrahlung (Abbildung 2 11 ] À -Anion handelt, das schon in vorangegangenen Untersuchungen gefunden wurde.…”

Chapter 1. In situ electron paramagnetic resonance (EPR) – a unique tool for analysing structure and reaction behaviour of paramagnetic sites in model and real catalysts

“…13). [93][94][95][96] The same species, though with slightly changed intensity ratios, are also formed in the presence of water. A possible formation pathway of these species is given in Scheme 3.…”

“…The assignment of the EPR signals is based on comparison of their g values with literature g values of known iron carbonyl anions. [93][94][95][96] In these previous studies, such radical anions were Fig. 12 Radical formation from the Fe 3 (CO) 12 WRC under reaction conditions.…”

“…The observed shfs constant A H ¼ 22.3 G agrees very well with that observed for the radical [HFe 2 (CO) 8 ] . 95 This radical, however, comprises only B3% of the total iron content. Nevertheless, it has been shown that the catalytic system is still active under these conditions.…”