Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
BCSJ Award Article
Investigation of Organoiron Catalysis in Kumada–Tamao–Corriu-Type Cross-Coupling Reaction Assisted by Solution-Phase X-ray Absorption Spectroscopy
Hikaru TakayaSho NakajimaNaohisa NakagawaKatsuhiro IsozakiTakahiro IwamotoRyuji ImayoshiNicholas J. GowerLaksmikanta AdakTakuji HatakeyamaTetsuo HonmaMasafumi TakagakiYusuke SunadaHideo NagashimaDaisuke HashizumeOsamu TakahashiMasaharu Nakamura
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Supplementary material

2015 Volume 88 Issue 3 Pages 410-418


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.

Solution-phase molecular structures of organoiron intermediates of Kumada–Tamao–Corriu-type cross-coupling were illuminated by X-ray absorption spectroscopy. The intermediacy of halomesityl iron complex of [FeIIBrMes(SciOPP)] and dimesityl iron complex of [FeIIMes2(SciOPP)] was adequately elucidated with formal nonredox FeII/FeII catalytic cycle. Fullsize Image
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© 2015 The Chemical Society of Japan
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