Organobismuth compounds with the pincer ligand 2,6-(Me2NCH2)2C6H3: Monoorganobismuth(iii) carbonate, sulfate, nitrate, and a diorganobismuthenium(iii) salt

Abstract

The reaction of RBiCl₂ (1) [R = 2,6-(Me₂NCH₂)₂C₆H₃] with Na₂CO₃ or Ag₂SO₄ (1 : 1 molar ratio) gave RBiCO₃ (2) and RBiSO₄ (3), respectively. RBi(NO₃)₂ (4) was obtained from RBiCl₂ and AgNO₃ (1 : 2 molar ratio). The ionic complex [R₂Bi][W(CO)₅Cl] (6) was obtained from R₂BiCl (5) and W(CO)₅(THF), following an unusual chlorine transfer from bismuth to tungsten. Compounds 2–4 are partially soluble in water. The molecular structures of 2·0.5CH₂Cl₂, 3, 4·H₂O and 6 were established by single-crystal X-ray diffraction. The carbonate 2 and the sulfate 3 exhibit a polymeric structure based on bridging oxo anions, while for the compound 4 dimer associations are formed, with both bridging and terminal nitrate anions. Dimer associations, based on weak Cl⋯H interactions between the cation and the anion, were found in the crystal of 6.