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Sequential iron(I)-mediated homologization of olefins by methanol and methyl halides in the gas phase

R. Wesendrup, C. A. Schalley, D. Schr”öder, H. Schwarz— 1996

The gas-phase chemistry of simple Fe(olefin)(+) complexes with CH(3)X (X = OH, F, Cl, Br, I) has been studied by Fourier-transform ion cyclotron resonance mass spectrometry. C-C bond formation between the alkene and CH(3)X occurs via initial insertion of Fe+ into the C-X bond, followed by a migratory insertion of the olefin into the iron-carbon bond of(X)-Fe(CH3)(+). This step constitutes a gas-phase analog of the initial stage in the Ziegler-Natta type C-C bond formation; a combination of subsequent beta-H shift and reductive elimination of HX completes the reaction. In the case of Fe(propene)(+) a remarkable regioselectivity is observed in that the addition results in the exclusive formation of an unbranched Fe(butene)(+) complex. Starting from Fe(ethene)(+), up to two consecutive methylations occur using CH3-. OH as a reactant; with methyl halides the number of methylations varies from 2 (for X = I) to 4 (for X = F). For alkyl halides RX bearing a beta-hydrogen, Fe+-mediated dehydrohalogenation of RX competes efficiently with the C-C coupling of RX and Fe(olefin)(+).

Title009
Sequential iron(I)-mediated homologization of olefins by methanol and methyl halides in the gas phase
AuthorR. Wesendrup, C. A. Schalley, D. Schr”öder, H. Schwarz
Date19960305
IdentifierDOI 10.1021/om950837g
Source(s)
CitationOrganometallics 1996, 15, 1435-1440
TypeText