Investigation of organoiron catalysis in Kumada-Tamao-Corriu-type cross-coupling reaction assisted by solution-phase X-ray absorption spectroscopy

Hikaru Takaya, Sho Nakajima, Naohisa Nakagawa, Katsuhiro Isozaki, Takahiro Iwamoto, Ryuji Imayoshi, Nicholas J. Gower, Laksmikanta Adak, Takuji Hatakeyama, Tetsuo Honma, Masafumi Takagaki, Yusuke Sunada, Hideo Nagashima, Daisuke Hashizume, Osamu Takahashi, Masaharu Nakamura

Research output: Contribution to journalArticle

30 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)410-418
Number of pages9
JournalBulletin of the Chemical Society of Japan
Volume88
Issue number3
DOIs
Publication statusPublished - 2015

Fingerprint

X ray absorption spectroscopy
Catalysis
X ray absorption
Metalloids
Geometry
Synchrotrons
Bromides
Paramagnetic resonance
Iron
Nuclear magnetic resonance
Oxidation
Chemical analysis

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Investigation of organoiron catalysis in Kumada-Tamao-Corriu-type cross-coupling reaction assisted by solution-phase X-ray absorption spectroscopy. / Takaya, Hikaru; Nakajima, Sho; Nakagawa, Naohisa; Isozaki, Katsuhiro; Iwamoto, Takahiro; Imayoshi, Ryuji; Gower, Nicholas J.; Adak, Laksmikanta; Hatakeyama, Takuji; Honma, Tetsuo; Takagaki, Masafumi; Sunada, Yusuke; Nagashima, Hideo; Hashizume, Daisuke; Takahashi, Osamu; Nakamura, Masaharu.

In: Bulletin of the Chemical Society of Japan, Vol. 88, No. 3, 2015, p. 410-418.

Research output: Contribution to journalArticle

Takaya, H, Nakajima, S, Nakagawa, N, Isozaki, K, Iwamoto, T, Imayoshi, R, Gower, NJ, Adak, L, Hatakeyama, T, Honma, T, Takagaki, M, Sunada, Y, Nagashima, H, Hashizume, D, Takahashi, O & 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, vol. 88, no. 3, pp. 410-418. https://doi.org/10.1246/bcsj.20140376
Takaya, Hikaru ; Nakajima, Sho ; Nakagawa, Naohisa ; Isozaki, Katsuhiro ; Iwamoto, Takahiro ; Imayoshi, Ryuji ; Gower, Nicholas J. ; Adak, Laksmikanta ; Hatakeyama, Takuji ; Honma, Tetsuo ; Takagaki, Masafumi ; Sunada, Yusuke ; Nagashima, Hideo ; Hashizume, Daisuke ; Takahashi, Osamu ; Nakamura, Masaharu. / Investigation of organoiron catalysis in Kumada-Tamao-Corriu-type cross-coupling reaction assisted by solution-phase X-ray absorption spectroscopy. In: Bulletin of the Chemical Society of Japan. 2015 ; Vol. 88, No. 3. pp. 410-418.
@article{80dceb0deba74ec8bafe5c881986d4bb,
title = "Investigation of organoiron catalysis in Kumada-Tamao-Corriu-type cross-coupling reaction assisted by solution-phase X-ray absorption spectroscopy",
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.",
author = "Hikaru Takaya and Sho Nakajima and Naohisa Nakagawa and Katsuhiro Isozaki and Takahiro Iwamoto and Ryuji Imayoshi and Gower, {Nicholas J.} and Laksmikanta Adak and Takuji Hatakeyama and Tetsuo Honma and Masafumi Takagaki and Yusuke Sunada and Hideo Nagashima and Daisuke Hashizume and Osamu Takahashi and Masaharu Nakamura",
year = "2015",
doi = "10.1246/bcsj.20140376",
language = "English",
volume = "88",
pages = "410--418",
journal = "Bulletin of the Chemical Society of Japan",
issn = "0009-2673",
publisher = "The Chemical Society of Japan",
number = "3",

}

TY - JOUR

T1 - Investigation of organoiron catalysis in Kumada-Tamao-Corriu-type cross-coupling reaction assisted by solution-phase X-ray absorption spectroscopy

AU - Takaya, Hikaru

AU - Nakajima, Sho

AU - Nakagawa, Naohisa

AU - Isozaki, Katsuhiro

AU - Iwamoto, Takahiro

AU - Imayoshi, Ryuji

AU - Gower, Nicholas J.

AU - Adak, Laksmikanta

AU - Hatakeyama, Takuji

AU - Honma, Tetsuo

AU - Takagaki, Masafumi

AU - Sunada, Yusuke

AU - Nagashima, Hideo

AU - Hashizume, Daisuke

AU - Takahashi, Osamu

AU - Nakamura, Masaharu

PY - 2015

Y1 - 2015

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84925426359&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84925426359&partnerID=8YFLogxK

U2 - 10.1246/bcsj.20140376

DO - 10.1246/bcsj.20140376

M3 - Article

AN - SCOPUS:84925426359

VL - 88

SP - 410

EP - 418

JO - Bulletin of the Chemical Society of Japan

JF - Bulletin of the Chemical Society of Japan

SN - 0009-2673

IS - 3

ER -