Intramolecularly Coordinated Group 14 and 15 Chalcogenites

The synthesis of N→M intramolecularly coordinated group 14 and 15 chalcogenites is reported. The N→Sn intramolecularly coordinated organotin­(IV) carbonate L­(Ph)­SnCO₃ (<b>1</b>), where L is the N,C,N-chelating ligand 2,6-(Me₂NCH₂)₂C₆H₃^–, reacts with SO₂ and SeO₂ to provide the organotin­(IV) sulfite L­(Ph)­SnSO₃ (<b>4</b>) and selenite [L­(Ph)­SnSeO₃]₂ (<b>5</b>), respectively. Treatment of [LSbO]₂ (<b>2</b>) and [LBiO]₂ (<b>3</b>) with SeO₂ provided the organoantimony and bismuth selenites LSbSeO₃ (<b>6</b>) and [LBiSeO₃]₃ (<b>7</b>), respectively. Compounds <b>5</b>–<b>7</b> are rare examples of mixed element oxides with well-defined stoichiometry MSeO₃ (M = Sn, Sb, Bi). Compounds <b>4</b>–<b>7</b> were characterized by means of elemental analyses, ¹H, ¹³C, ⁷⁷Se, and ¹¹⁹Sn NMR spectroscopies, IR spectroscopy, and single-crystal X-ray diffraction analysis