Synthesis and X−ray structures of thioxo− and selenoxo−phosphino species derived from monooxidation of new <i>N</i>-(4-acetylphenyl)-<i>P, P</i>-diphenylphosphinous amide ligand

2017-11-28T15:10:03Z (GMT) by Harbi Tomah Al-Masri Ziad Moussa
<p>The reaction of <i>p</i>-acetylaniline with chlorodiphenylphosphine afforded the new ligand (<i>p</i>-CH<sub>3</sub>CO)C<sub>6</sub>H<sub>4</sub>N(H)PPh<sub>2</sub> (<b>1</b>) in good yield. Monooxidized thioxo (<i>p</i>-CH<sub>3</sub>CO)C<sub>6</sub>H<sub>4</sub>N(H)P(S)Ph<sub>2</sub> (<b>2</b>) and selenoxo (<i>p</i>-CH<sub>3</sub>CO)C<sub>6</sub>H<sub>4</sub>N(H)P(Se)Ph<sub>2</sub> (<b>3</b>) were synthesized by the reaction of <b>1</b> with elemental sulfur or grey selenium. Compounds <b>1</b>–<b>3</b> were identified and characterized by multinuclear NMR spectroscopy (<sup>1</sup>H, <sup>13</sup>C, <sup>31</sup>P, <sup>77</sup>Se NMR) and elemental analysis. Compounds <b>2</b> and <b>3</b> were structurally characterized by single crystal X-ray diffraction which showed that the <i>p</i>-acetyl substituent on the aniline aromatic ring has a profound influence on the elongation of the P−N bond distance compared to several structurally characterized analogues found in literature. As such, subsequent reactions involving the P-N bond (i.e. insertion reactions) may be influenced in a favorable manner and proceed with ease.</p> <p></p>