R2BiOH (1) [R = 2-(Me2NCH2)C6H4] and (R2Bi)2O (2) are formed by hydrolysis of R2BiCl with KOH. Single crystals of 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 were determined by single-crystal X-ray diffraction.

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The reaction of RBiCl(2) (1) [R = 2,6-(Me(2)NCH(2))(2)C(6)H(3)] with Na(2)CO(3) or Ag(2)SO(4) (1 : 1 molar ratio) gave RBiCO(3) (2) and RBiSO(4) (3), respectively. RBi(NO(3))(2) (4) was obtained from RBiCl(2) and AgNO(3) (1 : 2 molar ratio). The ionic complex [R(2)Bi][W(CO)(5)Cl] (6) was obtained from R(2)BiCl (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 2·0.5CH(2)Cl(2), 3, 4·H(2)O 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.

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The hypercoordinated di‐ and triorganotin(IV) chlorides [{2‐(Me2NCH2)C6H4}2SnCl2] (1a) and [{2‐(Me2NCH2)C6H4}R2SnCl] [R = Me (2a), Ph (3a)] were prepared by treating SnCl4 or R2SnCl2 with [Li{2‐(Me2NCH2)C6H4}]. Halide‐exchange reactions between the organotin(IV) chlorides and the appropriate potassium halides gave [{2‐(Me2NCH2)C6H4}2SnX2] [X = F (1b), I (1d)], [{2‐(Me2NCH2)C6H4}Me2SnX] [X = F (2b), Br (2c), I (2d)] and [{2‐(Me2NCH2)C6H4}Ph2SnX] [X = F (3b), I (3d)]. Their solution behaviour was investigated by multinuclear (1H, 13C, 19F and 119Sn) NMR spectroscopy, including variable‐temperature studies. Single‐crystal X‐ray diffraction analyses revealed that the strong intramolecular coordination of the nitrogen atom from the pendant CH2NMe2 group to tin induces chirality. The influence of the identity and the number of the halogen atoms and the organic substituents at tin is discussed in relation with the hydrogen‐bonding network, which results in different supramolecular architectures in the crystal. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)