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  Elementary Steps of Iron Catalysis: Exploring the Links between Iron Alkyl and Iron Olefin Complexes for their Relevance in C—H Activation and C—C Bond Formation

Casitas, A., Krause, H., Goddard, R., & Fürstner, A. (2015). Elementary Steps of Iron Catalysis: Exploring the Links between Iron Alkyl and Iron Olefin Complexes for their Relevance in C—H Activation and C—C Bond Formation. Angewandte Chemie International Edition, 54(5), 1521-1526. doi:10.1002/anie.201410069.

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2015
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Wiley-VCH, 69451 Weinheim, Germany
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 Creators:
Casitas, Alicia1, Author              
Krause, Helga1, Author              
Goddard, Richard2, Author              
Fürstner, Alois1, Author              
Affiliations:
1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              
2Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              

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Free keywords: agostic interactions; C–H activation; cycloadditions; iron; homogeneous catalysi
 Abstract: The alkylation of complexes 2 and 7 with Grignard reagents containing β-hydrogen atoms is a process of considerable relevance for the understanding of C–H activation as well as C–C bond formation mediated by low-valent iron species. Specifically, reaction of 2 with EtMgBr under an ethylene atmosphere affords the bis-ethylene complex 1 which is an active precatalyst for prototype [2+2+2] cycloaddition reactions and a valuable probe for mechanistic studies. This aspect is illustrated by its conversion into the bis-alkyne complex 6 as an unprecedented representation of a cycloaddition catalyst loaded with two substrates molecules. On the other hand, alkylation of 2 with 1 equivalent of cyclohexylmagnesium bromide furnished the unique iron alkyl species 11 with a 14-electron count, which has no less than four β-H atoms but is nevertheless stable at low temperature against β-hydride elimination. In contrast, the exhaustive alkylation of 1 with cyclohexylmagnesium bromide triggers two consecutive C–H activation reactions mediated by a single iron center. The resulting complex has a diene dihydride character in solution (15), whereas its structure in the solid state is more consistent with an η3-allyl iron hydride rendition featuring an additional agostic interaction (14). Finally, the preparation of the cyclopentadienyl iron complex 25 illustrates how an iron-mediated C–H activation cascade can be coaxed to induce a stereoselective C—C bond formation. The structures of all relevant new iron complexes in the solid state are presented.

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Language(s): eng - English
 Dates: 2014-10-142014-12-102015-01-26
 Publication Status: Published in print
 Pages: 6
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/anie.201410069
 Degree: -

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Title: Angewandte Chemie International Edition
  Abbreviation : Angew. Chem. Int. Ed.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH Verlag GmbH & Co. KGaA
Pages: 6 Volume / Issue: 54 (5) Sequence Number: - Start / End Page: 1521 - 1526 Identifier: ISSN: 1521-3773
CoNE: https://pure.mpg.de/cone/journals/resource/0570-0833