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Title: Investigation of Organoiron Catalysis in Kumada–Tamao–Corriu-Type Cross-Coupling Reaction Assisted by Solution-Phase X-ray Absorption Spectroscopy
Authors: Takaya, Hikaru  kyouindb  KAKEN_id  orcid (unconfirmed)
Nakajima, Sho
Nakagawa, Naohisa
Isozaki, Katsuhiro  kyouindb  KAKEN_id  orcid (unconfirmed)
Iwamoto, Takahiro  kyouindb  KAKEN_id  orcid (unconfirmed)
Imayoshi, Ryuji
Gower, Nicholas J.
Adak, Laksmikanta
Hatakeyama, Takuji
Honma, Tetsuo
Takagaki, Masafumi
Sunada, Yusuke
Nagashima, Hideo
Hashizume, Daisuke
Takahashi, Osamu
Nakamura, Masaharu  kyouindb  KAKEN_id  orcid (unconfirmed)
Author's alias: 高谷, 光
中村, 正治
Issue Date: 2015
Publisher: Chemical Society of Japan
Journal title: Bulletin of the Chemical Society of Japan
Volume: 88
Issue: 3
Start page: 410
End page: 418
Abstract: 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.
Description: 放射光施設SPring-8で鉄触媒の作用を直接観察. 京都大学プレスリリース. 2015-03-16.
Rights: © 2015 The Chemical Society of Japan.
This is not the published version. Please cite only the published version. この論文は出版社版でありません。引用の際には出版社版をご確認ご利用ください。
DOI(Published Version): 10.1246/bcsj.20140376
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