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Dichloromethane (DCM), CH2Cl2 has been identified as an alternative reaction medium for room-temperature synthesis of subvalent homopolyatomic clusters of the group 15 element bismuth.

The binuclear palladium(I) compounds, [Pd-2(Ga2Cl7)(2)(C7H8)(2)] (1), [Pd-2(GaCl4)(2)(C9H12)(2)]center dot C9H12 (2) and [Pd-2(Ga2Cl7)(2)(C6H5Cl)(2)] (3), have been prepared from palladium(II) chloride in gallium(III) chloride-arene reaction media. All isolated crystalline solids (1, 2 and 3) have been structurally characterized by single crystal X-ray diffraction and Raman spectroscopy. The results form quantum chemical calculations on the interaction energies of the arenes and the dipalladium unit of these compounds is also presented.

[K(+)(2,2,2-crypt)] (2)Ge(9)(2-) containing the deltahedral Zintl anion Ge(9)(2-) has been isolated from a solution of K(4)Ge(9) in ethylenediamine in the presence of 2,2,2-crypt, intended as an intermediate in mixed-cluster synthesis. The subsequent crystallographic characterisation shows the closo-Ge(9)(2-) cluster unit to be tricapped trigonal-prismatic with a symmetry very close to D(3h). Each Ge(9)(2-) unit is surrounded by two 2,2,2-crypt units, each with a chelated K(+) cation, viz. [K(+)(2,2,2-crypt)]. The structure characterisation of this ordered Ge(9)(2-) cluster is surprisingly enough the first one reported. A chemical bonding analysis reveals two local minima of D(3h) symmetry, with that of lowest energy being highly similar to that resulting from the crystallographic analysis of low-temperature data. The cluster interaction scheme is based on highly delocalised bonding.

Following the development in the synthesis of subvalent cluster compounds, we report on the use of three different classes of room-temperature ionic liquids for the synthesis of the pentabismuth-tris(tetragallate) salt, Bi-5[GaCl4](3), characterized by X-ray diffraction. The Bi-5[GaCl4](3) salt was prepared by reduction of BiCl3 using gallium metal in ionic liquid reaction media containing a strong Lewis acid, GaCl3. The ionic liquids; trihexyltetradecyl phosphonium chloride [Th-Td-P+]Cl-, 1-dodecyl-3-methylimidazolium chloride [Dod-Me-Im(+)]Cl- and N-butyl-N-methylpyrrolidinium chloride [Bu-Me-Pyrr(+)]Cl- from three of the main classes of ionic liquids were used in synthesis. Reactions using ionic liquids composed of the trihexyltetradecyl phosphonium cation [Th-Td-P+] and the anions; tetrafluoroborate [BF4 (-)], bis(trifluoro-methyl sulfonyl) imide [(Tf)(2)N-] and hexafluorophosphate [PF6 (-)] were also investigated.