Rhodehouse, Melissa L., Bell, Thomas, Smetana, Volodyrnyr, Mudring, Anja-Verena and Meyer, Gerd H. (2018). From the Nonexistent Polar Intermetallic Pt3Pr4 via Pt2-xPr3 to Pt/Sn/Pr Ternaries. Inorg. Chem., 57 (16). S. 9949 - 9962. WASHINGTON: AMER CHEMICAL SOC. ISSN 1520-510X

Full text not available from this repository.

Abstract

Although the Pt-Pr phase diagram has been explored well, recent work on rare-earth metal cluster halides with endohedral transition metal atoms has provided a new binary intermetallic that is nonexistent in the known phase diagram: The binary Pt3Pr4 (1) crystallizes in a new structure type (mP56, P21/c, a = 12.353(2) angstrom, b = 7.4837(9) angstrom, c = 17.279(2) angstrom, beta = 118.003(7)degrees, z = 8) With six crystallographically independent Pt as well as eight Pr positions. The subsequent detailed investigation has led to another previously unreported, binary phase with the Ga2Gd3 structure type, Pt2-xPr3 (2, tI80, I4/mcm, a = 11.931(9) A, c = 14.45(1) angstrom, z = 16), that is practically overlapping with the rhombohedral Pt2Pr3 existing in the phase diagram. Application of different tin containing fluxes to reproduce the newly detected phases brought about two almost iso-compositional temary compounds with Sn, Pt4Sn6Pr2.91 (3), and Pt4.Sn6Pr3 (4), as well as Pt12Sn24Pr4.84 (5). 3 is a representative of the Pt4Ge6Ce3 type (oP52, Pnma, a = 7.2863(3) A, b = 4.4909(2) angstrom, c = 35.114(2) angstrom), while 4 represents a new variant of the prolific T4E6R3 family (T = transition metal, E = main group (semOrnetal, R = rare-earth metal; Pt4Sn6Pr3: oP52, Pnma, a = 27.623(1) angstrom, b = 4.5958(2) A, c = 9.3499(5) A). Pt(12)sn(24)Prs_x (5) crystallizes as a variant of the Ni8Sn16Gd3 type (cI82, /m(-3), a = 12.274(1) A, z = 2). Electronic structure calculations provide hints on the origin of the structural changes (pseudo-polymorphism) for PtxPr3 with x = 1.97 and 2.00, respectively, and reveal that heteroatomic Pt-Pr bonding strongly dominates in both binaries while the addition of the reactive metal tin leads to dominating Pt-Sn bonding interactions in the ternaries; Pt Pt bonding interactions are strong but represent a minority in the binaries and are not present at all in the ternaries.

Item Type: Journal Article
Creators:
CreatorsEmailORCIDORCID Put Code
Rhodehouse, Melissa L.UNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Bell, ThomasUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Smetana, VolodyrnyrUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Mudring, Anja-VerenaUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Meyer, Gerd H.UNSPECIFIEDUNSPECIFIEDUNSPECIFIED
URN: urn:nbn:de:hbz:38-176209
DOI: 10.1021/acs.inorgchem.8b01121
Journal or Publication Title: Inorg. Chem.
Volume: 57
Number: 16
Page Range: S. 9949 - 9962
Date: 2018
Publisher: AMER CHEMICAL SOC
Place of Publication: WASHINGTON
ISSN: 1520-510X
Language: English
Faculty: Unspecified
Divisions: Unspecified
Subjects: no entry
Uncontrolled Keywords:
KeywordsLanguage
TOTAL-ENERGY CALCULATIONS; CRYSTAL-STRUCTURE; RARE-EARTH; GADOLINIUM SESQUICHLORIDE; CLUSTER IODIDES; METALS; PHASE; GOLD; LA; PRMultiple languages
Chemistry, Inorganic & NuclearMultiple languages
Refereed: Yes
URI: http://kups.ub.uni-koeln.de/id/eprint/17620

Downloads

Downloads per month over past year

Altmetric

Export

Actions (login required)

View Item View Item