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Structural, Theoretical and Multinuclear NMR Study of a New Polymeric Mercury(II) Complex with an Ambidentate Phosphorus Ylide

The reactions of phosphorus ylides of the type Ph3P=C(H)C(O)R [R = 2,4-dichlorophenyl (L 1 ) and 4-isopropylphenyl (L 2 )] with HgX2 [X = Cl (1, 4), Br (2, 5) and I (3, 6)] salts using methanol as a solvent are reported. Single crystal X-ray analysis carried out on L 1 , 2 and 3 and reveals the presence of a novel polymeric structure for 2 and a centrosymmeteric dimeric structure for 3. The complexes have been studied by elemental analyses, IR, 1H and 31P NMR spectroscopy. On the basis of DFT calculations, the formation of [Hg2Br6]2− anions in 2 has a key role in the formation of the polymeric structure; and, the formation of [Hg2L2I4] molecule thermodynamically is about 25 kcal/mol more favorable than the corresponding [Hg2L2Br4] molecule.

Authors:   Seyyed Javad Sabounchei, Mehdi Sarlakifar, Mahbubeh Pourshahbaz, Sadegh Salehzadeh, Mehdi Bayat, Hamid Reza Khavasi, Fatemeh Akhlaghi Bagherjeri, Collete Boscovic
Journal:   Journal of Inorganic and Organometallic Polymers and Materials
Year:   2012
Pages:   1
DOI:   10.1007/s10904-012-9793-6
Publication date:   07-Nov-2012
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