Structural studies on iminophosphine ligands and their palladium complexes |
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Authors: | Bandoli Giuliano Dolmella Alessandro Crociani Laura Antonaroli Simonetta Crociani Bruno |
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Affiliation: | (1) Dipartimento di Scienze Farmaceutiche, Università di Padova, Via Marzolo 5, 35131 Padova, Italy;(2) Dipartimento di Chimica Fisica, Università di Padova, Via Loredan, 35131 Padova, Italy;(3) Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata , Via della Ricerca Scientifica, 00133 Roma, Italy;(4) Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata , Via della Ricerca Scientifica, 00133 Roma, Italy |
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Abstract: | The crystal and molecular structures of the iminophosphine o-(Ph2P)C6H4CH=NC6H4OMe-4 (1) and its palladium complexes [Pd( 3-C3H5){o-(Ph2P)C6H4CH=NC6H4OMe-p}]BF4 (2) and [Pd( 2-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 2-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( 2-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. |
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