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  Triple Resonance Experiments for the Rapid Detection of 103Rh NMR Shifts: A Combined Experimental and Theoretical Study into Dirhodium and Bismuth–Rhodium Paddlewheel Complexes

Caló, F. P., Bistoni, G., Auer, A. A., Leutzsch, M., & Fürstner, A. (2021). Triple Resonance Experiments for the Rapid Detection of 103Rh NMR Shifts: A Combined Experimental and Theoretical Study into Dirhodium and Bismuth–Rhodium Paddlewheel Complexes. Journal of the American Chemical Society, 143(32), 12473-12479. doi:10.1021/jacs.1c06414.

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ja1c06414_si_001.pdf (Supplementary material), 7MB
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 Creators:
Caló, Fabio P.1, Author           
Bistoni, Giovanni2, Author           
Auer, Alexander A.3, Author           
Leutzsch, Markus4, Author           
Fürstner, Alois1, Author           
Affiliations:
1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              
2Research Group Bistoni, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541703              
3Research Group Auer, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541705              
4Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445623              

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 Abstract: A H(C)Rh triple resonance NMR experiment makes the rapid detection of 103Rh chemical shifts possible, which were previously beyond reach. It served to analyze a series of dirhodium and bismuth–rhodium paddlewheel complexes of the utmost importance for metal–carbene chemistry. The excellent match between the experimental and computed 103Rh shifts in combination with a detailed analysis of the pertinent shielding tensors forms a sound basis for a qualitative and quantitative interpretation of these otherwise (basically) inaccessible data. The observed trends clearly reflect the influence exerted by the equatorial ligands (carboxylate versus carboxamidate), the axial ligands (solvents), and the internal “metalloligand” (Rh versus Bi) on the electronic estate of the reactive Rh(II) center.

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Language(s): eng - English
 Dates: 2021-06-212021-08-052021-08-18
 Publication Status: Published in print
 Pages: 7
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.1c06414
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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: 143 (32) Sequence Number: - Start / End Page: 12473 - 12479 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870