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  Experimental and Theoretical Investigations of New Dinuclear Palladium Complexes as Precatalysts for the Amination of Aryl Chlorides

Christmann, U., Pantazis, D. A., Benet-Buchholz, J., McGrady, J. E., Maseras, F., & Vilar, R. (2006). Experimental and Theoretical Investigations of New Dinuclear Palladium Complexes as Precatalysts for the Amination of Aryl Chlorides. Journal of the American Chemical Society, 128(19), 6376-6390. doi:10.1021/ja057825z.

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 Creators:
Christmann, Ute1, 2, Author
Pantazis, Dimitrios A.3, Author              
Benet-Buchholz, Jordi1, Author
McGrady, John E.4, Author
Maseras, Feliu1, 5, Author
Vilar, Ramón2, Author
Affiliations:
1Institute of Chemical Research of Catalonia (ICIQ), 43007 Tarragona, Spain, ou_persistent22              
2Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ, U.K., ou_persistent22              
3Department of Chemistry, University of York, Heslington, York YO10 5DD, U.K., ou_persistent22              
4WestCHEM, Department of Chemistry, UniVersity of Glasgow, G12 8QQ, U.K., ou_persistent22              
5Unitat de Química Física, Edifici Cn, UniVersitat Autònoma de Barcelona, 08193 Bellaterra, Spain, ou_persistent22              

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 Abstract: A series of new palladium dinuclear species with general formula [Pd2X(μ-X){μ- PtBu2(Bph-R)}] (X = Cl, Br; Bph = biphenyl; R = H, Me, NMe2) have been prepared. The two palladium centers in these species are bridged by one of the aromatic rings of the biphenyl group present in the corresponding phosphine. The X-ray crystal structure of one of these complexes has been obtained, providing a clear picture of the bonding pattern. The stability of these dimers in solution is shown to be highly dependent on the nature of the phosphine R group and also on the bridging halide. When R = NMe2, the dimers dissociate, yielding the palladium(II) compounds PdX2{PtBu2(BPh-NMe2)} (X = Cl, Br), and the X-ray crystal structure of one of them (X = Br) has shown that the biphenyl group from the phosphine interacts directly with the metal center. This interaction seems to play an important role in stabilizing the otherwise coordinatively unsaturated palladium(II) complex. In contrast, when R = H or Me, the analogous monomeric palladium(II) complexes are unstable and undergo cyclometalation to generate a palladium(II) dinuclear species in which each of the two phosphines cyclometalates with the palladium centers forming a strained four-membered ring. In addition to their unusual structures, these aryl-bridged dimers have also proven to be excellent precatalysts for the amination of aryl chlorides. To rationalize some of the experimental results, a detailed DFT computational study has been carried out and is presented herein.

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Language(s): eng - English
 Dates: 2005-11-172006-04-152006-05-01
 Publication Status: Published in print
 Pages: 15
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ja057825z
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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: 128 (19) Sequence Number: - Start / End Page: 6376 - 6390 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870