Synthesis of alkali metal indium thiophosphates containing the discrete anions [In(PS4)(PS5)2]6- and [In(PS4)2(PS5)]6-

Alexander Rothenberger; Collin Morris; Mercouri G. Kanatzidis

doi:10.1021/ic100495b

Synthesis of alkali metal indium thiophosphates containing the discrete anions [In(PS₄)(PS₅)₂]^6- and [In(PS₄)₂(PS₅)]^6-

Alexander Rothenberger, Collin Morris, Mercouri G. Kanatzidis

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	5598-5602
Number of pages	5
Journal	Inorganic chemistry
Volume	49
Issue number	12
DOIs	https://doi.org/10.1021/ic100495b
State	Published - Jun 21 2010
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic100495b

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@article{eef1c7bd19a64ca1970dc84fef368ed0,

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 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.",

author = "Alexander Rothenberger and Collin Morris and Kanatzidis, {Mercouri G.}",

year = "2010",

month = jun,

day = "21",

doi = "10.1021/ic100495b",

language = "English (US)",

volume = "49",

pages = "5598--5602",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

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T1 - Synthesis of alkali metal indium thiophosphates containing the discrete anions [In(PS4)(PS5)2]6- and [In(PS4)2(PS5)]6-

AU - Rothenberger, Alexander

AU - Morris, Collin

AU - Kanatzidis, Mercouri G.

PY - 2010/6/21

Y1 - 2010/6/21

N2 - 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.

AB - 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.

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Synthesis of alkali metal indium thiophosphates containing the discrete anions [In(PS₄)(PS₅)₂]^6- and [In(PS₄)₂(PS₅)]^6-

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