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  Reductive Elimination of C6F5–C6F5 from Pd(II) Complexes: Influence of α-Dicationic Chelating Phosphines

Gu, L., Wolf, L. M., Thiel, W., Lehmann, C. W., & Alcarazo, M. (2018). Reductive Elimination of C6F5–C6F5 from Pd(II) Complexes: Influence of α-Dicationic Chelating Phosphines. Organometallics, 37(5), 665-672. doi:10.1021/acs.organomet.7b00418.

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om7b00418_si_001.pdf (Supplementary material), 3MB
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NMR spectra and detailed computational results
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Cartesian coordinates for crystallographic structures
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 Creators:
Gu, Lianghu1, Author
Wolf, Lawrence M.2, Author
Thiel, Walter3, Author              
Lehmann, Christian W.4, Author              
Alcarazo, Manuel1, Author
Affiliations:
1Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077 Göttingen, Germany, ou_persistent22              
2Department of Chemistry, University of Massachusetts Lowell, Lowell, Massachusetts 01854, United States, ou_persistent22              
3Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              
4Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              

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 Abstract: We report the synthesis and characterization through NMR and X-ray techniques of a series of [Pd(C6F5)2(PP)] complexes constituted by diphosphine chelating ligands of different nature and evaluate the rates for the challenging reductive elimination of C6F5–C6F5. By virtue of their very weak donor properties, dicationic ancillary ligands effectively promote the desired transformation. Density functional theory (DFT) calculations were performed to rationalize these findings. The Pd(0)-complexes formed after the elimination step could not be isolated because the Pd(0) center has a tremendous tendency to insert into one of the P–C+ bonds of the α-cationic ligands rendering Pd(II)-phosphinidene complexes. The same behavior was observed for Ni(0) species.

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Language(s): eng - English
 Dates: 2017-06-062017-07-252018-03-12
 Publication Status: Published in print
 Pages: 8
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.organomet.7b00418
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Title: Organometallics
  Other : Organometallics
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 37 (5) Sequence Number: - Start / End Page: 665 - 672 Identifier: ISSN: 0276-7333
CoNE: https://pure.mpg.de/cone/journals/resource/954925505259