ISSN:
0009-2940
Keywords:
Bond activation
;
Oxygen atom transfer
;
Iron oxenoid chemistry
;
Rate constants
;
Ion cyclotron resonance mass spectrometry
;
Ligand effects
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The presence of a benzene ligand in Fe(C6H6)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-(C6H6)O+ + X → Fe(X)O+ + 6H6) follows two principally different pathways. For X = C6D6 and C5H5N 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 Fe6H6)O+. The resulting intermediate (6H6)Fe(OX)+ will then fall apart either to separated Fe(OX)+/6H6) or to Fe(6H6)+/OX, thus bringing about an epoxidation of the olefin rather than ketone formation.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19941271222
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