期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 57, 期 22, 页码 6496-6500出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201802087
关键词
cross-coupling; iron; MCD spectroscopy; Mossbauer spectroscopy; N-methylpyrrolidone
资金
- National Institutes of Health [R01GM111480]
- NSF Graduate Research Fellowship
- Alfred P. Sloan Fellowship
- Ruth L. Kirchstein National Research Service award [F32GM120823]
The use of N-methylpyrrolidone (NMP) as a co-solvent in ferric salt catalyzed cross-coupling reactions is crucial for achieving the highly selective, preparative scale formation of cross-coupled product in reactions utilizing alkyl Grignard reagents. Despite the critical importance of NMP, the molecular level effect of NMP on in situ formed and reactive iron species that enables effective catalysis remains undefined. Herein, we report the isolation and characterization of a novel trimethyliron(II) ferrate species; [Mg(NMP)(6)][FeMe3](2) (1), which forms as the major iron species in in (actions of Fe(acac)(3) and MeMgBr under catalytically relevant conditions where NMP is employed as a co-solvent. Importantly, combined GC analysis and Fe-57 Mossbauer spectroscopic identified 1 us a highly reactive iron species for the selective formation generating cross-coupled product. These studies demonstrate that NMP does not directly interact with iron as a ligand in catalysis but, alternatively, interacts with the magnesium cations to preferentially stabilize the formation of 1 over [Fe8Me12](-) cluster generation, which occurs in the absence of NMP.
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