R₂BiOH (1) [R = 2-(Me₂NCH₂)C₆H₄] and (R₂Bi)₂O (2) are formed by hydrolysis of R₂BiCl with KOH. Single crystals of 2 were obtained by air oxidation of (R₂Bi)₂. The reaction of R₂BiCl and Na₂CO₃ leads to (R₂Bi)₂CO₃ (3). 3 is also formed by the absorption of CO₂ from the air in solutions of 1 or 2 in diethyl ether or toluene. (R₂Bi)₂S (4) is obtained from R₂BiCl and Na₂S or from (R₂Bi)₂ and S₈. Exchange reactions between R₂BiCl and KBr or NaI give R₂BiX [X = Br (5), I (6)]. The reaction of RBiCl₂ (7) with Na₂S and [W(CO)₅(THF)] gives cyclo-(RBiS)₂[W(CO)₅]₂ (8). cyclo-(R′BiS)₂ (9) [R′ = 2,6-(Me₂NCH₂)₂C₆H₃] is formed by reaction of R′BiCl₂ and Na₂S. The structures of 1–9 were determined by single-crystal X-ray diffraction.

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.