[Ag(PPh3)4][(PPh3)CdCl3], the first monomeric trichlorocadmate complex bonded to a phosphorus ligand: A structural and spectroscopic study in solution and solid state

• Published in: Inorganic chemistry communications 2016-08, Vol.70, p.35-40
• Main Authors: Priola, Emanuele, Bonometti, Elisabetta, Rabezzana, Roberto, Buscaino, Roberto, Chierotti, Michele R., Operti, Lorenza, Diana, Eliano
• Format: Article
• Language: English
• Subjects: Cadmium; DFT; ESI mass spectrometry; Luminescence; Silver; XRD structure
• ISSN: 1387-7003; 1879-0259
• DOI: 10.1016/j.inoche.2016.05.011

The complex [Ag(PPh3)4][(PPh3)CdCl3] was synthesized and its crystal structure was determined. Solid state properties of the complex were further studied by 31P SS-NMR, Raman and IR spectroscopies. This compound presents one of the rare cases of monomeric trichlorocadmate, the first reported with a phosphorus ligand. We can obtain this thanks to the use of a big spherical cation like [Ag(PPh3)4]+. In the same time we analyze the structural effects that govern the crystallochemistry of analogous compounds. The absorption and emission properties of this compound in the solid state were analyzed by a computational modeling. For the rarity of the complex, we use the ESI-MS and 31P NMR techniques to check the properties of this anion in ethanolic solution, and the results are useful to evaluate the stability of [(PPh3)CdCl3]− ion and the role of [Ag(PPh3)4]+ ion in organizing the crystal structure during the crystal growth. The bulky pseudo-spherical [Ag(PPh3)4]+ ion is able to stabilize in the solid state the [(PPh3)CdCl3]− complex. [Display omitted] •A new, unusual trichlorocadmate complex of cadmium has been prepared.•A NMR and ESI-MS analysis has been performed to study the anion stability.•His stability relies on crystal packing forces.