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  Enhanced Electrophilicity of Heterobimetallic Bi–Rh Paddlewheel Carbene Complexes: A Combined Experimental, Spectroscopic, and Computational Study

Collins, L. R., van Gastel, M., Neese, F., & Fürstner, A. (2018). Enhanced Electrophilicity of Heterobimetallic Bi–Rh Paddlewheel Carbene Complexes: A Combined Experimental, Spectroscopic, and Computational Study. Journal of the American Chemical Society, 140(40), 13042-13055. doi:10.1021/jacs.8b08384.

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 Creators:
Collins, Lee R.1, Author              
van Gastel, Maurice2, Author              
Neese, Frank3, Author              
Fürstner, Alois1, Author              
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1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              
2Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541713              
3Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              

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 Abstract: Dirhodium paddlewheel complexes are indispensable tools in modern organometallic catalysis for the controlled decomposition of diazo-compounds. Tuning the reactivity of the thus-formed transient carbenes remains an active and dynamic field of research. Herein, we present our findings that the distal metal center plays an as yet underappreciated role in modulating this reactivity. Replacement of one rhodium atom in the bimetallic core for bismuth results in the formation of a significantly more electrophilic carbene complex. Bismuth-rhodium catalysts thereby facilitate previously unknown modes of reactivity for α-diazoester compounds, including the cyclopropanation of alkenes as electron deficient as trichloroethylene. While dirhodium paddlewheel complexes remain the catalysts of choice for many carbene-mediated transformations, their bismuth-rhodium analogues exhibit complementary reactivity and show great potential for small molecule and solvent activation chemistry. DFT calculations highlight the importance of metal–metal bonding interactions in controlling carbene electrophilicity. The paucity of these interactions between the 4d orbitals of rhodium and the 6p orbitals of bismuth results in weaker π-back-bonding interactions for bismuth-rhodium carbene complexes compared to dirhodium carbene complexes. This leads to weakening of the rhodium-carbene bond and to a more carbene-centered LUMO, accounting for the observed enhancement in bismuth-rhodium carbene electrophilicity. These findings are supported by a detailed spectroscopic study of the “donor–donor” carbene complexes Rh2(esp)2C(p-MeOPh)2 (19) and BiRh(esp)2C(p-MeOPh)2 (20), employing a combination of UV–vis and resonance Raman spectroscopy. The results reveal that carbene chemoselectivity in MRh(L)4 catalysis can be modulated to a previously unrecognized extent by the distal metalloligand.

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Language(s): eng - English
 Dates: 2018-08-062018-09-142018-10-10
 Publication Status: Published in print
 Pages: 14
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.8b08384
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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 140 (40) Sequence Number: - Start / End Page: 13042 - 13055 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870