The first discrete anionic indium thiophosphate complexes are reported. The structures of K6[In(PS4)1.5(PS 5)1.5] (1), Rb6[In(PS4)(PS 5)2] (2), and Cs6[In(PS4) 1.5(PS5)1.5] (3) all contain an anionic moiety consisting of octahedrally coordinated indium surrounded by the thiophosphate anions [PS4]3- and the new [PS5]3- ion. The conformation and bonding of the unsymmetric chelate ligand [PS 5]3- to indium give rise to different anions of the general formula [In(PS4)1+x(PS5) 2-x]6- (x = 0, 0.5). The anionic moiety in K 6[In(PS4)1.5(PS5)1.5] (1) consists of cocrystallizing λ-[In(PS4)2(PS 5)]6- and Λλδ-[In(PS 4)(PS5)2]6- anions in a ratio of 1:1 (and their enantiomers). In Rb6[In(PS4)(PS 5)2] (2), no cocrystallizatzion of anions was observed, and only the Λλλ-[In(PS4)(PS5) 2]6- anion (and its enantiomer) is present. Cs 6[In(PS4)1.5(PS5)1.5] (3) shows the same disorder between [PS4]3- and [PS 5]3- ions as in 1. In 3, however, the octahedrally coordinated indium atom and thiophosphate ligands form a Λδδ- [In(PS4)(PS5)2]6- anion cocrystallizing with δ-[In(PS4)2(PS 5)]6-. Additionally, ordered Rb6[In(PS 4)(PS5)2] (2) was characterized by 31P magic angle spinning NMR, Raman spectroscopy, UV-vis solid-state absorption spectroscopy, thermogravimetric analysis, differential thermal analysis, and energy dispersive X-ray analysis.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry