Oxygen atom transfer from {mu}-Oxo-bis[1,4,8,11,15,18,22,25-octakis(trifluoromethyl)ph-thalocya ninato]diiron(III) : evidence for an Fe(IV)=O intermediate.
The dimeric [(FPc)Fe]2({mu}-O) (1) (FPc is the dianion of 1,4,8,11,15,18,22,25-octakis(trifluoromethyl)phthalocyanine) has been shown to transfer its -oxo atom quantitatively to trimethylphosphine and triphenylphosphine. In the case of triphenylphosphine a base such as 1-methylimidazole (MeIm) or pyridine (py) is needed to induce the oxygen atom transfer. The reaction of 1 with MeIm at -40 C and below gives [(MeIm)(FPc)Fe]2({mu}-O) (4), which disproportionates to give (MeIm)2(FPc)Fe (5) and (FPc)Fe=O (6) at higher temperatures. The oxo atom of 6 has been shown to transfer to triphenylphosphine. Similarly, 6 is generated by the disproportionation of 1 with py. It has also been generated by the oxidation of 1 with t-butyl hydroperoxide. [(FPc)Fe]2({mu}-O) catalyzes the oxidation of hydrocarbons by iodosylbenzene. With stilbenes, styrenes, cyclohexenes and butenes as substrates, both epoxidations and alkyl C-H bond oxidations have been observed. The epoxidation of cis-stilbene leads to a mixture of cis- and trans-stilbene oxides, indicating that epoxidation of cis-stilbene, and possibly other olefins as well, proceeds through a non-concerted mechanism.
- Research Organization:
- Argonne National Laboratory (ANL)
- DOE Contract Number:
- AC02-06CH11357
- OSTI ID:
- 938153
- Report Number(s):
- ANL/CMT/JA-27609
- Journal Information:
- J. Porphyrins Phthalocyanines, Journal Name: J. Porphyrins Phthalocyanines Journal Issue: 6 ; 1998 Vol. 2
- Country of Publication:
- United States
- Language:
- ENGLISH
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