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Tris(pyrazolyl)phosphine Oxides. Synthesis and Coordination Chemistry with Copper(I)

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posted on 23.04.2012, 00:00 by Cornelis G. J. Tazelaar, Volodymyr Lyaskovskyy, Tom van Dijk, Daniël L. J. Broere, Ludo A. Kolfschoten, Rima Osman Hassan Khiar, Martin Lutz, J. Chris Slootweg, Koop Lammertsma
A set of substituted tris­(pyrazolyl)­phosphine oxides (OP­(pzx)3) has been prepared in high yield and applied as neutral scorpion-type ligands. The P apex provides a convenient spectroscopic handle. Substitution at the 3-position of the pyrazolyl ring influences the steric demands of the ligand, while substitution at the 5-position enhances the stability. Copper­(I) acetonitrile complexes of the OP­(pzx)3 ligands were prepared and tested in ligand exchange reactions with PPh3 and CO. The ν­(CO) values of the carbonyl complexes demonstrate the electron-withdrawing properties of the ligands. These observations show that OP­(pzx)3 ligands are an interesting extension of the widely used scorpion-type ligands.