Premium
Dissociation Patterns of Small Fe m O n + ( m = 1–4, n ⩽ 6) Cluster Cations Formed Upon Chemical Ionization of Fe(CO) 5 /O 2 Mixtures
Author(s) -
Schröder Detlef,
Jackson Phillip,
Schwarz Helmut
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(200006)2000:6<1171::aid-ejic1171>3.0.co;2-w
Subject(s) - chemistry , dissociation (chemistry) , cluster (spacecraft) , ionization , inorganic chemistry , chemical ionization , ion , organic chemistry , computer science , programming language
The collisional activation mass spectra of cationic iron oxide clusters Fe m O n + ( m = 1–4, n ⩽ 6) prepared by chemical ionization of Fe(CO) 5 /O 2 mixtures show remarkable trends in the fragmentation behaviors, which can be attributed to the formal oxidation states of iron. (i) The preferential fragmentation pathways of Fe m O n + clusters with m / n ⩾ 1 correspond to losses of atomic oxygen as well as FeO units. (ii) For Fe m O n + clusters with 1 > m / n > 2/3, losses of neutral FeO 2 begin to compete with those of O and FeO. (iii) For FeO 2 + and the oxygen‐rich clusters Fe 2 O 3 + and Fe 4 O 6 + ( m/n = 2/3), losses of molecular oxygen predominate, while this channel is more or less irrelevant for the other Fe m O n + cations. These observations are interpreted using peroxide structures for the oxygen‐rich Fe m O n + ions, thereby preventing the need for formal high‐valent iron(IV) in these clusters.