| Abstract: | The reaction between BiI3 and two equivalents of dmpu (dmpu = N,N′-dimethylpropylene urea) in thf (tetrahydrofuran) or toluene affords dark red crystals of the complex Bi(dmpu)6]Bi3I12] which was characterised by X-ray crystallography and consists of octahedral Bi(dmpu)6]3+ cations and Bi3I12]3? anions both with 3 symmetry. An analogous reaction between SbI3 and dmpu afforded orange crystals of what is probably a hydrolysis product, C5NH6]2H(dmpu)2]Sb2I9], which was also characterised by X-ray crystallography and contains a face-shared bioctahedral Sb2I9]3? anion with two pyridinium cations and a hydrogen bonded H(dmpu)2]+ cation. CH2?C(C6H4-4-NO2)CH2NMe3]I and one equivalent of SbI3 afforded the orange crystalline complex CH2?C(C6H4-4-NO2)CH2NMe3]3Sb2I9] an X-ray crystallographic study of which revealed a face-shared bioctahedral Sb2I9]3? anion similar to that present in C5NH6]2H(dmpu)2]Sb2I9]. Four equivalents of BiI3 and CH2?C(C6H4-4-NO2)CH2NMe3]I afforded the complex CH2?C(C6H4-4-NO2)CH2NMe3]3Bi3I12], the Bi3I12]3? anion being essentially identical to that encountered in Bi(dmpu)6]Bi3I12]. CH3(CH2)2COS(CH2)2NMe3]I and four equivalents of SbI3 yielded orange crystals of the complex CH3(CH2)2COS(CH2)2NMe3]4Sb8I28] which was also characterised by X-ray crystallography and shown to contain a new structural type of E8X28]4? anion (E = As, Sb, Bi; X = halide). |
