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Reactivity Tuning by Ligand Effects: Gas‐Phase Reactions of Fe(C 6 H 6 )O + versus “Bare” FeO +
Author(s) -
Stöckigt Detlef,
Schwarz Helmut
Publication year - 1994
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19941271222
Subject(s) - chemistry , reactivity (psychology) , ligand (biochemistry) , olefin fiber , reagent , medicinal chemistry , metal , oxygen , benzene , crystallography , ketone , substitution reaction , oxide , oxygen atom , stereochemistry , inorganic chemistry , catalysis , molecule , organic chemistry , medicine , biochemistry , receptor , alternative medicine , pathology
The presence of a benzene ligand in Fe(C 6 H 6 )O + (1) has a profound effect on the gas‐phase reactivity of FeO + . While the latter oxide is known to act as an efficient C‐H/C‐C bond‐activation reagent, the ligated species 1 is entirely unreactive in that respect. However, 1 serves as an excellent reagent for transferring oxygen to various olefins. In addition, it is demonstrated that the ligand substitution Fe‐(C 6 H 6 )O + + X → Fe(X)O + + 6 H 6 ) follows two principally different pathways. For X = C 6 D 6 and C 5 H 5 N the traditional direct substitution process with attack at the metal centre is operative. However, for X = olefins it is argued that the olefin will not initially attack the metal center; rather, the reaction commences by coordinating the olefin X to the oxygen atom of Fe 6 H 6 )O + . The resulting intermediate ( 6 H 6 )Fe(OX) + will then fall apart either to separated Fe(OX) + / 6 H 6 ) or to Fe( 6 H 6 ) + /OX, thus bringing about an epoxidation of the olefin rather than ketone formation.