Pd and Pt metal atoms as electron donors in s-hole bonded complexes

Quantum calculations provide a systematic assessment of the ability of Group 10 transition metals M = Pd and Pt to act as an electron donor within the context of pnicogen, chalcogen, and halogen bonds. These M atoms are coordinated in a square planar geometry, attached to two N atoms of a modified phenanthrene unit, as well as two ligand atoms Cl, Br, or I. As the Lewis acid, a series of AF(n) molecules were chosen, which could form a pnicogen bond (A = P, As, Sb), chalcogen bond (A = S, Se, Te) or halogen bond (A = Cl, Br, I) with M. These noncovalent bonds are fairly strong, varying between 6 and 20 kcal mol(-1), with the occupied d(z)(2) orbital of M acting as the origin of charge transferred to the acid. Pt forms somewhat stronger bonds than Pd, and the bond strength rises with the size of the A atom of the acid. Within the context of smaller A atoms, the bond strength rises in the order pnicogen < chalcogen < halogen, but this distinction vanishes for the fifth-row A atoms. The nature of the ligand atoms on M has little bearing on the bond strength. Based on the Harmonic Oscillator Model of Aromaticity (HOMA) index, the ZB, YB and XB bonds were shown to have only a subtle effect on the ring electronic structures.

Automated summary

In this study, the ability of Pd and Pt to act as electron donors within the context of pnicogen, chalcogen, and halogen bonds was systematically assessed through quantum calculations. The results showed that Pt forms stronger bonds than Pd, and the bond strength is correlated with the size of the A atom of the acid.