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Arylarsonate- and Phosphonate-Capped Polyoxomolybdates, [(RC<sub>6</sub>H<sub>4</sub>As)<sub>2</sub>Mo<sub>6</sub>O<sub>24</sub>]<sup><i>n</i>−</sup> and [(R′C<sub>6</sub>H<sub>4</sub>P)<sub>2</sub>Mo<sub>5</sub>O<sub>21</sub>]<sup><i>n</i>−</sup>
14
Citations
39
References
2021
Year
We report on the synthesis and structural characterization of four arylarsonate- and phosphonate-capped polyoxomolybdates that exhibit different organic substituents in the para position of the phenyl group. The reaction of arylarsonates (RAsO<sub>3</sub>, wherein R = 4-BrC<sub>6</sub>H<sub>4</sub> or 4-N<sub>3</sub>C<sub>6</sub>H<sub>4</sub>) with molybdate in aqueous pH 3.5 media resulted in the cyclic hexamolybdates [(BrC<sub>6</sub>H<sub>4</sub>As)<sub>2</sub>Mo<sub>6</sub>O<sub>24</sub>]<sup>4-</sup> (<b>Mo</b><sub><b>6</b></sub><b>As</b><sub><b>2</b></sub><b>L</b><sub><b>a</b></sub>) and [(N<sub>3</sub>C<sub>6</sub>H<sub>4</sub>As)<sub>2</sub>Mo<sub>6</sub>O<sub>24</sub>]<sup>4-</sup> (<b>Mo</b><sub><b>6</b></sub><b>As</b><sub><b>2</b></sub><b>L</b><sub><b>b</b></sub>), whereas the reaction of arylphosphonates (R'PO<sub>3</sub>, wherein R' = 4-O<sub>2</sub>CC<sub>6</sub>H<sub>4</sub> or 4-O<sub>2</sub>CC<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>) with molybdate in aqueous pH 3 media resulted in the cyclic pentamolybdates [(O<sub>2</sub>CC<sub>6</sub>H<sub>4</sub>P)<sub>2</sub>Mo<sub>5</sub>O<sub>21</sub>]<sup>6-</sup> (<b>Mo</b><sub><b>5</b></sub><b>P</b><sub><b>2</b></sub><b>L</b><sub><b>c</b></sub>) and [(HO<sub>2</sub>CC<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>P)<sub>2</sub>Mo<sub>5</sub>O<sub>21</sub>]<sup>4-</sup> (<b>Mo</b><sub><b>5</b></sub><b>P</b><sub><b>2</b></sub><b>L</b><sub><b>d</b></sub>), respectively. Polyanions <b>Mo</b><sub><b>6</b></sub><b>As</b><sub><b>2</b></sub><b>L</b><sub><b>a</b></sub> and <b>Mo</b><sub><b>6</b></sub><b>As</b><sub><b>2</b></sub><b>L</b><sub><b>b</b></sub> comprise a ring of six MoO<sub>6</sub> octahedra that is capped on either side by an organoarsonate group, whereas <b>Mo</b><sub><b>5</b></sub><b>P</b><sub><b>2</b></sub><b>L</b><sub><b>c</b></sub> and <b>Mo</b><sub><b>5</b></sub><b>P</b><sub><b>2</b></sub><b>L</b><sub><b>d</b></sub> consist of a ring of five MoO<sub>6</sub> octahedra that is capped on either side by an organophosphonate group, with the organic arms protruding away from the metal-oxo core of the polyanions. All four polyanions <b>Mo</b><sub><b>6</b></sub><b>As</b><sub><b>2</b></sub><b>L</b><sub><b>a</b></sub>, <b>Mo</b><sub><b>6</b></sub><b>As</b><sub><b>2</b></sub><b>L</b><sub><b>b</b></sub>, <b>Mo</b><sub><b>5</b></sub><b>P</b><sub><b>2</b></sub><b>L</b><sub><b>c</b></sub>, and <b>Mo</b><sub><b>5</b></sub><b>P</b><sub><b>2</b></sub><b>L</b><sub><b>d</b></sub> have been characterized in the solid state by single-crystal X-ray diffraction, IR spectroscopy, and thermogravimetric and elemental analysis and in solution by multinuclear NMR (<sup>31</sup>P, <sup>13</sup>C, and <sup>1</sup>H). The synthetic procedure of (4-bromophenyl)arsonic acid, BrC<sub>6</sub>H<sub>4</sub>AsO<sub>3</sub>H<sub>2</sub>, is reported here for the first time.
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