The preparation and characterization of a platinum ether complex |
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Authors: | H.C. Clark S.S. McBride N.C. Payne C.S. Wong |
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Affiliation: | Department of Chemistry, The University of Western Ontario, London, Ontario N6A 5B7 Canada |
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Abstract: | The reaction of [Pt((F3C)CCH(CF3))(P(C2H5)3)2CH3OH]PF6 with allene in methanol affords a novel metallocyclic ethereal complex [CH3)(P(C2H5)3)2]PF6, which has been characterized by 1H, 2H, 19F and 31P NMR spectroscopy. Its structure has also been determined by a single crystal X-ray analysis. The crystal are monoclinic, space group P21/n, with cell dimensions a 20.012(5), b 17.222(5), c 8.902(3) Å and β 91.54(5)°. The structure was refined by full matrix least-squares methods on F, using 3097 unique observations collected by automated four circle diffractometer. Refinement converged at R 0.066. The Pt atom has a distorted square-planar coordination geometry, with cis P atoms, and PtP distances of 2.219(4) Å (trans to O) and 2.324(4) Å (trans to C). These results show the ethereal group is a weak ligand to platinum(II) but because of the chelating effect, its displacement by other ligands is thermodynamically not favorable. The mechanism of formation of the ethereal complex is also discussed. |
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