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Transition Metal Chemistry

, Volume 25, Issue 1, pp 17–25 | Cite as

Structural studies on iminophosphine ligands and their palladium complexes

  • Giuliano Bandoli
  • Alessandro Dolmella
  • Laura Crociani
  • Simonetta Antonaroli
  • Bruno Crociani
Article

Abstract

The crystal and molecular structures of the iminophosphine o-(Ph2P)C6H4CH=NC6H4OMe-4 (1) and its palladium complexes [Pd(η3-C3H5){o-(Ph2P)C6H4CH=NC6H4OMe-p}]BF4 (2) and [Pd(η2-fn){o-(Ph2P)C6H4CH=NC6H4OMe-4}] [fn = fumaronitrile, (3)] have been determined by X-ray analysis. In the free ligand (1), the planar imino group of E configuration is oriented, relative to the PPh2 unit, so that the CH=N hydrogen atom points towards phosphorus, with the nitrogen atom on the opposite side. In (2) and (3) the iminophosphine behaves as a P,N-chelate ligand, this coordination mode being achieved by the imino group rotation of 169.3 ° and 145.3 °, respectively, around its bond with the ortho disubstituted phenyl ring. Complex (2) shows a structural disorder with two different orientations of the allyl ligand. The trigonal planar coordination around the central metal in complex (3) involves the P- and N-donor atoms of (1) and the η2-bound olefin, with a marked lengthening of the olefinic carbon-carbon bond. In both the complexes, the chelate six-membered ring of the iminophosphine with palladium is not coplanar with the N-Pd-P coordination plane, the imino carbon atom and the ortho disubstituted phenyl group lying on the same side out of the N-Pd-P plane, whereas the N-substituent and one of the PPh2 groups are on the opposite side. The 1H-n.m.r. spectra at low temperatures of (2) and (3), and of [Pd(η2-tmetc){o-(Ph2P)C6H4CH=NCMe3}] [tmetc = tetramethyl ethylenetetracarboxylate, (4)] are interpreted on the basis of a non-rigid conformation of the chelate iminophosphine, which undergoes a fast dynamic process whereby the N- and P-substituents move above and below the coordination plane.

Keywords

Palladium Allyl Imino Tetramethyl Coordination Plane 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Kluwer Academic Publishers 2000

Authors and Affiliations

  • Giuliano Bandoli
    • 1
  • Alessandro Dolmella
    • 1
  • Laura Crociani
    • 2
  • Simonetta Antonaroli
    • 3
  • Bruno Crociani
    • 4
  1. 1.Dipartimento di Scienze FarmaceuticheUniversità di Padova, Via Marzolo 5PadovaItaly
  2. 2.Dipartimento di Chimica FisicaUniversità di Padova, Via LoredanPadovaItaly
  3. 3.Dipartimento di Scienze e Tecnologie ChimicheUniversità di Roma ‘Tor Vergata’, Via della Ricerca ScientificaRomaItaly
  4. 4.Dipartimento di Scienze e Tecnologie ChimicheUniversità di Roma ‘Tor Vergata’, Via della Ricerca ScientificaRoma, Italy

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