Polynuclear Chalcogenide-Centered Complexes with Metallophilic Interactions

In the last decade a great dealt of attention has been paid to the chemistry of polynuclear gold derivatives with a central heteroatom, not only from the experimental and structural but also from the theoretical standpoint (1). Interesting hypercoordinated species of the type [C(AuPR3)5]+, [C(AuPR3)6]2+, [N(AuPR3)5]2+, [P(AuPR3)5]2+ and [P(AuPR3)6]3+ have been described (2), apart from other complexes with more conventional stoichiometry, and all have in common the presence of gold-gold interactions of ca. 3 Å. Usually, the chemistry of the first row elements of the p-block is known to follow classical rules of bonding, and only in cases of extreme electron-deficiency has the traditional electron count to be reconsidered to account for special types of molecular or solid state structures. Many of these heteroatomcentered complexes are electron-deficient and the gold-gold interactions provide a significant contribution to their stability. The attraction between these closed-shell systems has recently captured the attention in inorganic and organometallic chemistry (1). P. Pyykkö has summarized the available theoretical and experimental evidence of intra- and inter-molecular interactions between heavy metal atoms, such as Au(I) (3). In general, when heavy metals are involved in such interaction, the closed-shell attractions are of metallophilic or van der Waals type, as has been found for d8, d10 coinage-metals, and d10s2 centers. Experimental evidence for the aurophilic Au(I)???Au(I) attraction is available from crystallography, NMR and Raman spectroscopies, and optical spectroscopic measurements of the interaction strength (4). It is manifested in molecular conformations with relatively close Au???Au interactions of ca. 3 Å, whose strength has been estimated at ca. 25-50 kJ/mol (5). These attractions are weaker than most covalent or ionic bonds, but stronger than other van der Waals bonds and comparable in strength to typical hydrogen bonds. The phenomenon cannot be satisfactorily explained by classical theories such as hybridization (3). From a theoretical point of view, the attractions close to equilibrium distances are caused by dispersive interactions together with relativistic effects (6). The attractive contributions are dominated by pair-excitations from the heavy metal, such as gold, strengthened by relativistic effects. In all the cases where there are inter- or intramolecular metal-metal attractions, the correlation effects are essential; if they are omitted, at the Hartree-Fock (HF) level, repulsive interactions are obtained (6). Hence, it is necessary to use at least second-order Møller-Plesset level (MP2) methods for the dispersive forces, which are included in the electronic correlation effects (7).