Regium Bonds between Silver(I) Pyrazolates Dinuclear Complexes and Lewis Bases (N₂, OH₂, NCH, SH₂, NH₃, PH₃, CO and CNH)

• Main Authors: Ibon Alkorta, Cristina Trujillo, Goar Sánchez-Sanz, José Elguero
• Format: Article
• Language: English
• Published: MDPI AG 2020-02-01
• Series: Crystals
• Subjects: non-covalent interactions; regium bonds; silver(i); coinage metals; pyrazolates; phosphines
• Online Access: https://www.mdpi.com/2073-4352/10/2/137
• ISSN: 2073-4352

A theoretical study and Cambridge Structural Database (CSD) search of dinuclear Ag(I) pyrazolates interactions with Lewis bases were carried out and the effect of the substituents and ligands on the structure and on the aromaticity were analyzed. A relationship between the intramolecular Ag−Ag distance and stability was found in the unsubstituted system, which indicates a destabilization at longer distances compensated by ligands upon complexation. It was also observed that the asymmetrical interaction with phosphines as ligands increases the Ag−Ag distance. This increase is dramatically higher when two simultaneous PH₃ ligands are taken into account. The calculated ¹⁰⁹Ag chemical shielding shows variation up to 1200 ppm due to the complexation. Calculations showed that six-membered rings possessed non-aromatic character while pyrazole rings do not change their aromatic character significantly upon complexation.