The elucidation of formation mechanisms is mandatory for understanding and planning of synthetic routes. For (bio-)organic and organometallic compounds, this has long been realized even for very complicated molecules, whereas the formation of ligand-free inorganic molecules has widely remained a black box to date. This is due to poor structural relationships between reactants and products and the lack of structurally related intermediates—due to the comparably high coordination flexibility of involved atoms. Here we report on investigations of the stepwise formation of multimetallic clusters, based on a series of crystal structures and complementary quantum-chemical studies of (Ge2As2)2−, (Ge7As2)2−, [Ta@Ge6As4]3−, [Ta@Ge8As4]3− and [Ta@Ge8As6]3−. The study makes use of efficient quantum-chemical tools, enabling the first detailed screening of the energy hypersurface along the formation of ligand-free inorganic species for a semi-quantitative picture. The results can be generalized for an entire family of multimetallic clusters.

Homobimetallic metallophilic interactions between copper, silver, and gold-based [(NHC)MX]-type complexes (NHC=N-heterocyclic carbene, i.e, 1,3,4-trimethyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene; X=F, Cl, Br, I) were investigated by means of ab initio interaction energies, Ziegler-Rauk-type energy-decomposition analysis, the natural orbital for chemical valence (NOCV) framework, and the noncovalent interaction (NCI) index. It was found that the dimers of these complexes predominantly adopt a head-to-tail arrangement with typical M⋅⋅⋅M distance of 3.04-3.64 Å, in good agreement with the experimental X-ray structure determined for [{(NHC)AuCl}2 ], which has an Au⋅⋅⋅Au distance of 3.33 Å. The interaction energies between silver- and gold-based monomers are calculated to be about -25 kcal mol(-1) , whereas that for the Cu congener is significantly lower (-19.7 kcal mol(-1) ). With the inclusion of thermal and solvent contributions, both of which are destabilizing, by about 15 and 8 kcal mol(-1) , respectively, an equilibrium process is predicted for the formation of dimer complexes. Energy-decomposition analysis revealed a dominant electrostatic contribution to the interaction energy, besides significantly stabilizing dispersion and orbital interactions. This electrostatic contribution is rationalized by NHC(δ(+) )⋅⋅⋅halogen(δ(-) ) interactions between monomers, as demonstrated by electrostatic potentials and derived charges. The dominant NOCV orbital indicates weakening of the π backdonation in the monomers on dimer formation, whereas the second most dominant NOCV represents an electron-density deformation according to the formation of a very weak M⋅⋅⋅M bond. One of the characteristic signals found in the reduced density gradient versus electron density diagram corresponds to the noncovalent interactions between the metal centers of the monomers in the NCI plots, which is the manifestation of metallophilic interaction.

The properties of various electron-deficient germylenes and stannylenes are investigated using density functional theory (DFT). The dominant electrophilic character of these divalent group IV compounds is demonstrated by computed DFT-based reactivity descriptors. Next, the interaction of selected model dihalogenated germylenes and stannylenes (GeX2 and SnX2, with X = F, Cl, Br, I) with a series of potential aromatic π-donors is studied; computed classical donor–acceptor σ-interactions with strong Lewis bases serve as a reference. In addition, natural bond orbital analyses were performed in order to study the interactions at the orbital level, consistently indicating that the most important interaction for the π-complexations is the overlap of the formal empty p-orbital on the germanium or the tin atom and the π-orbitals of the aromatic rings. Additional information is obtained from the extent of charge transfer from the π-donors toward the divalent tin and germanium compounds. The existence of a complexation interaction between the π-clouds of the aromatic rings and the divalent compounds is theoretically established. The strength of the π-complexation parallels the trends in electron-donating and electron-withdrawing character of the substituents on the aromatic compounds. Correlations of the total complexation energy with the NBO interaction energy confirm that this π-complexation is essentially an orbital-controlled interaction. In agreement with experimental data, σ-complexation is found to dominate over π-complexation.

Reaction of the binary Zintl anion (Sn2 Sb2 )(2-) with the β-diketiminato complex [LCu(NCMe)] (L=nacnac=[(N(C6 H3 (i) Pr2 -2,6)C(Me))2 CH](-) ) in ethylenediamine or DMF affords the ternary cluster dimer {[CuSn5 Sb3 ](2-) }2 (1) as its [K(crypt-222)](+) salt. The chemical formulation of 1 is supported by energy-dispersive X-ray spectroscopy (EDX) and quantum chemical calculations. Each monomeric part of the dimer represents a trimetallic "[CuSn5 Sb3 ](2-) " cluster, with an architecture in between a tricapped trigonal prism and a capped square antiprism. As shown by quantum chemical investigations, the presence of Sb atoms and, in particular, of Cu atoms in the cluster skeleton makes the monomeric unit behave like an inhomogeneous superatom, which clearly prefers to dimerize, thereby producing a relatively short, yet virtually non-bonding Cu⋅⋅⋅Cu distance.