title: Synthesis of alkali metal indium thiophosphates containing the discrete anions [In(PS4)(PS5)2]6- and [In(PS4)2(PS5)]6-.
abstract: The first discrete anionic indium thiophosphate complexes are reported. The structures of K(6)[In(PS(4))(1.5)(PS(5))(1.5)] (1), Rb(6)[In(PS(4))(PS(5))(2)] (2), and Cs(6)[In(PS(4))(1.5)(PS(5))(1.5)] (3) all contain an anionic moiety consisting of octahedrally coordinated indium surrounded by the thiophosphate anions [PS(4)](3-) and the new [PS(5)](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(PS(4))(1+x)(PS(5))(2-x)](6-) (x = 0, 0.5). The anionic moiety in K(6)[In(PS(4))(1.5)(PS(5))(1.5)] (1) consists of cocrystallizing lambda-[In(PS(4))(2)(PS(5))](6-) and Lambdalambdadelta-[In(PS(4))(PS(5))(2)](6-) anions in a ratio of 1:1 (and their enantiomers). In Rb(6)[In(PS(4))(PS(5))(2)] (2), no cocrystallizatzion of anions was observed, and only the Lambdalambdalambda-[In(PS(4))(PS(5))(2)](6-) anion (and its enantiomer) is present. Cs(6)[In(PS(4))(1.5)(PS(5))(1.5)] (3) shows the same disorder between [PS(4)](3-) and [PS(5)](3-) ions as in 1. In 3, however, the octahedrally coordinated indium atom and thiophosphate ligands form a Lambdadeltadelta-[In(PS(4))(PS(5))(2)](6-) anion cocrystallizing with delta-[In(PS(4))(2)(PS(5))](6-). Additionally, ordered Rb(6)[In(PS(4))(PS(5))(2)] (2) was characterized by (31)P magic angle spinning NMR, Raman spectroscopy, UV-vis solid-state absorption spectroscopy, thermogravimetric analysis, differential thermal analysis, and energy dispersive X-ray analysis.
authors.affiliation: Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA.
authors.forename: Alexander
authors.initials: A
authors.lastname: Rothenberger
authors.forename: Collin
authors.initials: C
authors.lastname: Morris
authors.forename: Mercouri G
authors.initials: MG
authors.lastname: Kanatzidis
mesh_terms: D000838:Anions / Q000737:chemistry; D007204:Indium / Q000737:chemistry*; D008672:Metals, Alkali / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010710:Phosphates / Q000737:chemistry*
chemical_list: D000838:Anions; D008672:Metals, Alkali; D009942:Organometallic Compounds; D010710:Phosphates; D007204:Indium; C035638:thiophosphoric acid