DFT‐based calculations reveal that the global minimum of IrB12‐ is a C3v symmetric bowl‐like structure in which the Ir atom is located on the concave side of the bowl similar to its lighter congeners, CoB12‐ and RhB12‐.

A series of clusters with the general formula CBe(5)E(-) (E = Al, Ga, In, Tl) are theoretically shown to have a planar pentacoordinate carbon atom. The structures show a simple and rigid topological framework-a planar EBe(4) ring surrounding a C center, with one of the ring Be-Be bonds capped in-plane by a fifth Be atom. The system is stabilized by a network of multicenter σ bonds in which the central C atom is the acceptor, and π systems as well by which the C atom donates charge to the Be and E atoms that encircle it.

Can relativistic effects modify the NICS and the B(ind) values? In this manuscript we evaluate the relativistic corrections incorporated via the zeroth-order regular approximation to the calculations of nucleus-independent chemical shifts and the induced magnetic field (B(ind)) in the E12(2-) spherenes (E = Ge, Sn, Pb). We found that both electron delocalization descriptors are strongly affected by the relativistic corrections. For instance, for plumbaspherene, the difference in values from the nonrelativistic to the relativity-included calculation is almost 40 ppm! Our results show that the changes observed in the NICS and B(ind) values in the title cages are a consequence of the treatment of the relativistic effects. If these effects are included as scalar or spin-orbit calculations, then we can establish the next trend: Ge12(2-) is a nonaromatic species, Sn12(2-) is a low aromatic species, and Pb12(2-) is strongly aromatic, according to calculated NICS and B(ind) values. Thus, any prediction of electron delocalization in molecules containing heavy elements without considering an adequate treatment for relativistic effects may lead to an erroneous chemical interpretation.

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We report a combined experimental–theoretical study on the 31P NMR chemical shift for a number of trans-platinum(ii) complexes.