The off-symmetrical structure of the toluene⋯SbCl₃ complex is a consequence of the off-centre location of σ-holes at the Sb atom. DFT-SAPT calculations have been used to determine the total interaction energies and their components. The characteristic features of the pnicogen bonding are due to the concert action of electrostatic and dispersion interactions.

The reactivity of (L^CN)₂Sn (1) (where L^CN is 2-(N,N-dimethylaminomethyl)phenyl-) towards various substrates containing E–Cl bond(s) has been studied (E = C, Si, Ge and Sn). Alkyl chlorides like chloroform or dichloromethane reacts with 1 to form (L^CN)₂SnCl₂ and unidentified by-products in poor yields. The reaction of benzoyl chloride with 1 at low temperature yielded a thermally unstable product (L^CN)₂Sn(Cl)C(O)Ph (2) which was isolated and characterized by both multinuclear NMR spectroscopy and X-ray diffraction techniques. The vicinity of the central tin atom in 2 reveals trigonal bipyramidal geometry. Attempts to oxidize 2 by dioxygen to give the corresponding organotin(IV) benzoate failed. On the other hand, the reaction of the in situ prepared (L^CN)₂SnO (synthesized by the reaction of 1 with dioxygen) with PhCOCl resulted in the formation of the desired organotin(IV) benzoate (L^CN)₂Sn(Cl)C(O)OPh (3). The reaction of 1 with Ph₃GeCl yielded triphenylgermyl-substituted diorganotin(IV) chloride (L^CN)₂Sn(Cl)GePh₃ (4) which subsequently gave mixed diorganotin(IV) chloride-oxide [(L^CN)₂SnCl]₂O (5) upon loss of the GePh₃ moiety in the air. When the same reaction was carried out in benzene instead of chloroform a unique [Ph₃Ge]₄[Sn₆O₈] cluster (6) was obtained. Similarly, the reaction of 1 with Ph₃SiCl provided triphenylsilyl-substituted diorganotin(IV) chloride (L^CN)₂Sn(Cl)SiPh₃ (7) which was then oxidized to (L^CN)₂Sn(Cl)OSiPh₃ (8). The unprecedented reaction of 1 with (n-Bu)₃SnCl provided the distannane (L^CN)₂Sn(Cl)SnBu₃ (9) which could be oxidized by dioxygen to a distannoxane (L^CN)₂Sn(Cl)OSnBu₃ (10). In addition, the solid-state structures of 3, 5, 6 and 8 were determined by the X-ray diffraction techniques.

Reactions of lithiated cobalt bis(1,2-dicarbollide)(1⁻) anion (1⁻) in presence of paraformaldehyde, ethylene oxide or trimethylene oxide led to the substitution of 1⁻ at the C-atoms resulting in the high yield formation of monosubstituted alkylhydroxy derivatives [(1-HO(CH₂)_n-1,2-C₂B₉H₁₀)(1′,2′-C₂B₉H₁₁)-3,3′-Co(III)]⁻ (n = 1–3) isolated as caesium salts (Cs2, Cs3, Cs4) along with disubstituted products of general formulation [(HO(CH₂)_n-1,2-C₂B₉H₁₀)₂-3,3′-Co(III)]⁻ (n = 1–3) (Cs5, Cs6 and Cs7). Disubstituted compounds are in fact a mixture of diastereoisomers denoted as 1,1′-anti(rac-), 1,2′-syn- and in case of Cs6 and Cs7 also 1,2-vicinal-isomer, from which only the anti-isomer could be isolated in pure form in case of shorter chain compounds Cs5 and Cs6. All these alkylhydroxy derivatives can serve as versatile precursors for the generation of a variety of functional molecules. Thus, reaction of Me₃NH4 with NaH and one equivalent of POCl₃ provided after hydrolysis the phosphorylated [(1-(HO)₂P(O)OC₃H₆-1,2-C₂B₉H₁₀)(1′,2′-C₂B₉H₁₁)-3,3′-Co(III)]⁻ derivative, isolated in the form of trimethylammonium salt, Me₃NH8 as the main product whereas reaction with half of the equivalent produces a high yield of phosphoric acid diester (Me₃NH)₂9 comprising in its structure two cages connected via propyl spacers to the central part. The calcium salt Ca(10)₂ of bridged ion [μ-(HOP(O)(OC₃H₆)₂)-(1,2-C₂B₉H₁₀)₂-3,3′-Co(III)]⁻ resulted from reaction of Me₃NH7 with NaH and one equivalent of POCl₃ followed by hydrolysis and addition of CaCl₂. All new compounds were characterized by multinuclear NMR spectroscopy and mass spectrometry and the structure of Me₃NH3 and that of the respective salts of the pure anti-stereoisomer of dialkylhydroxy derivatives Cs5 and Me₃NH6 were established by X-ray crystallography.