Solution-phase synchrotron X-ray absorption spectroscopy (XAS) is a powerful tool for structural and mechanistic investigations of paramagnetic organoiron intermediates in solution-phase reactions. For paramagnetic organotransition metal intermediates, difficulties are often encountered with conventional NMR- and EPR-based analyses. By using solution-phase XAS, we succeeded in identifying the organoiron species formed in the reaction of iron bisphosphine with mesitylmagnesium bromide, MesMgBr, and 1-bromodecane in a [FeX2(SciOPP)]-catalyzed Kumada-Tamao-Corriu (KTC)-type cross-coupling reaction. X-ray absorption near-edge structure (XANES) spectra showed that the resulting aryliron species possessed a divalent oxidation state. Extended X-ray absorption fine structure (EXAFS) demonstrated that the solution-phase molecular geometries of these species are in satisfactory agreement with the crystallographic geometries of [FeIIBrMes(SciOPP)] and [FeIIMes2(SciOPP)]. By combining GC-quantitative analysis and solution-phase XAS, the cross-coupling reactivities of these aryliron species were successfully investigated in the reaction with 1- bromodecane under stoichiometric and catalytic conditions.
CITATION STYLE
Takaya, H., Nakajima, S., Nakagawa, N., Isozaki, K., Iwamoto, T., Imayoshi, R., … Nakamura, M. (2015). Investigation of organoiron catalysis in Kumada-Tamao-Corriu-type cross-coupling reaction assisted by solution-phase X-ray absorption spectroscopy. Bulletin of the Chemical Society of Japan, 88(3), 410–418. https://doi.org/10.1246/bcsj.20140376
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