期刊
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
卷 88, 期 3, 页码 410-418出版社
CHEMICAL SOC JAPAN
DOI: 10.1246/bcsj.20140376
关键词
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资金
- Funding Program for Next generation World-Leading Researchers (Next Program)
- Council for Science and Technology Policy (CSTP)
- CREST from Japan Science and Technology Agency (JST) [1102545, 11103784]
- Ministry of Education, Culture, Sports, Science and Technology (MEXT) [22550099]
- Sumitomo Fellowship program
- JSPS [24.02790, 24.02338]
- [JSPS]
- Grants-in-Aid for Scientific Research [26888009, 12F02338, 26288036, 15K04755, 15K13694, 24685011, 26410118, 22550099, 25108003] Funding Source: KAKEN
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 axyliron 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 [Fe(II)BrMes(SciOPP)] and [Fe(II)Mes(2)(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.
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