Electron-transfer chemistry of the 20-electron complex (Fe sup 0 (C sub 6 Me sub 6 ) sub 2 ) and of the 19-electron complex (Fe sup I (C sub 6 Me sub 6 )(. eta. sup 5 -C sub 6 Me sub 6 H)): Mild C-H activation by O sub 2 via superoxide ion and functionalization of the exocyclic methylenes in the resulting complexes (Fe sup 0 (C sub 6 Me sub 6 )(. eta. sup 4 -polyene))

Journal Article · Sun Jul 01 00:00:00 EDT 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00157a029· OSTI ID:6379583

Astruc, D; Ardoin, N ^[1]; Mandon, D; Madonik, A; Michaud, P ^[2]; Varret, F ^[3]

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1. Universite de Bordeaux I, Talence (France)
2. Universite de Rennes I (France)
3. Universite du Maine, Le Mans (France)

Activation of methyl substituents by mild reactions with O{sub 2} has been achieved in paramagnetic bis(arene)iron complexes and followed by functionalization of the nucleophilic exocyclic methylene groups. The 20e complex (Fe{sup 0}(C{sub 6}Me{sub 6}){sub 2}) (2), best synthesized from (Fe{sup II}(C{sub 6}Me{sub 6}){sub 2}){sup 2+} (PF{sub 6}{sup {minus}}){sub 2} (1) and Na/Hg in THF at 20{degree}C, shows a Moessbauer doublet with isomer shift IS = 1.02 mm s{sup {minus}1} vs Fe and quadrupole splitting QS = {minus}1.35 mm s{sup {minus}1} (293 K). It reacts at {minus}40{degree}C with 1/2 mol of O{sub 2} in toluene to give the thermally unstable o-xylylene complex (Fe{sup 0}(C{sub 6}Me{sub 6})({eta}{sup 4}-C{sub 6}Me{sub 4}({double bond}CH{sub 2}){sub 2})) (4), characterized by NMR spectroscopy in C{sub 6}d{sub 5}CD{sub 3} at {minus}50{degree}C.

• OSTI ID: 6379583
• Journal Information: Organometallics; (USA), Vol. 9:7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AROMATICS
CHEMICAL ACTIVATION
DATA ANALYSIS
ELECTRON TRANSFER
EXPERIMENTAL DATA
MEASURING INSTRUMENTS
MEASURING METHODS
SUPEROXIDE RADICALS
DATA
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
RADICALS
400201* - Chemical & Physicochemical Properties