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  Structures of Reactive Donor/Acceptor and Donor/Donor Rhodium Carbenes in the Solid State and Their Implications for Catalysis

Werlé, C., Goddard, R., Philipps, P., Farès, C., & Fürstner, A. (2016). Structures of Reactive Donor/Acceptor and Donor/Donor Rhodium Carbenes in the Solid State and Their Implications for Catalysis. Journal of the American Chemical Society, 138(11), 3797-3805. doi:10.1021/jacs.5b13321.

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Werlé, Christophe1, Author              
Goddard, Richard2, Author              
Philipps, Petra3, Author              
Farès, Christophe3, 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              
3Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445623              

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 Abstract: Owing to its tremendous preparative importance, rhodium carbene chemistry has been studied extensively during past decades. The invoked intermediates have, however, so far proved too reactive for direct inspection, and reliable experimental information has been extremely limited. A series of X-ray structures of pertinent intermediates of this type, together with supporting spectroscopic data, now closes this gap and provides a detailed picture of the constitution and conformation of such species. All complexes were prepared by decomposition of a diazoalkane precursor with an appropriate rhodium source; they belong to either the dirhodium(II) tetracarboxylate carbene series that enjoys widespread preparative use, or to the class of mononuclear half-sandwich carbenes of Rh(III), which show considerable potential. The experimental data correct or refine previous computational studies but corroborate the currently favored model for the prediction of the stereochemical course of rhodium catalyzed cyclopropanations, which is likely also applicable to other reactions. Emphasis is put on stereoelectronic rather than steric arguments, with the dipole of the acceptor substituent flanking the carbene center being the major selectivity determining factor. Moreover, the very subtle influence exerted by the anionic ligands on a Rh(III) center on the chemical character of the resulting carbenes species is documented by the structures of a homologous series of halide complexes. Finally, the isolation of a N-bonded Rh(II) diazoalkane complex showcases that steric hindrance represents an inherent limitation of the chosen methodology.

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Language(s): eng - English
 Dates: 2015-12-212016-02-242016-03-23
 Publication Status: Published in print
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.5b13321
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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 138 (11) Sequence Number: - Start / End Page: 3797 - 3805 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870