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.

Complex [Au(C6F5)2][Bi(C6H4CH2NMe(2)-2)2] displays the first example of an interaction between Au(I) and Bi(III), the nature of which is shown to be consistent with the presence of a high ionic contribution (79%) and a dispersion type (van der Waals) interaction (21%).

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.

The homoleptic [2‐{E(CH2CH2)2NCH2}C6H4]3Bi [E = O (1), MeN (2)], the chlorides [2‐{E(CH2CH2)2NCH2}C6H4]2BiCl [E = O (3), MeN (4)] and the dichlorides [2‐{E(CH2CH2)2NCH2}C6H4]BiCl2 [E = O (5), MeN (6)] were synthesized by reaction of the corresponding ortho‐lithium derivative with BiCl3 in corresponding molar ratios. The dihalides [2‐{E(CH2CH2)2NCH2}C6H4]BiX2 [X = Br, E = O (7), MeN (9); X = I, E = O (8), MeN (10)] as well as [2‐(Me2NCH2)C6H4]BiBr2 (11) were obtained by halide exchange reactions between RBiCl2 and excess aqueous solution of KX. The compounds were characterized by multinuclear (1H, 13C) NMR spectroscopy and mass spectrometry. The crystal and molecular structures of 1–5 and 11 were determined by single‐crystal X‐ray diffraction. In all compounds the (C6H4CH2)N nitrogen atoms are coordinated to bismuth. The crystals of 1 and 2, as well as those of the chlorides 3 and 4, contain discrete molecules. For R3Bi intramolecular N→Bi interactions of medium strength [Bi(1)–N(1) 3.170(7) Å for 1 and 3.211(5) Å for 2] result in an overall distorted octahedral (C,N)3Bi core. In the monochlorides one nitrogen atom is strongly coordinated to the bismuth atom [2.660(11) Å for 3 and 2.744(14) Å for 4] trans to the halogen atom, whereas the second one is involved in a weaker intramolecular N→Bi interaction [3.095(11) Å for 3 and 3.061(14) Å for 4] trans to a carbon atom. The overall (C,N)2BiCl core is distorted square‐pyramidal. The crystals of the monohalides 5 and 11 contain discrete dimer units. The pendant arm nitrogen atom is strongly coordinated [2.548(9) Å for 5 and 2.485(13) Å for 11] trans to the bridging halogen atom, thus resulting in an overall distorted square‐pyramidal (C,N)BiX3 (X = Cl, Br) core. The six‐membered morpholinyl and piperazinyl rings in 1–5 adopt the chair conformation, which prevents intramolecular coordination of the oxygen or N(Me) nitrogen atoms to bismuth. Supramolecular architectures based on intermolecular Bi···Br interactions, Cl···H, and Br···H contacts are formed in the crystals of 3, 5, and 11.