Electronic and Structural Properties of MPtₓB₆-₂ₓ (M = Y, Yb): Structural Disorder in an Octahedral Boron Framework

Abstract

Two new ternary platinum borides, YPtxB6-2x and YbPtxB6-2x, were obtained by argon-arc melting of the elements followed by annealing at 780 °C (750 °C). The structures of these compounds combine the fragments of CaB6- and AuCu3-type structures [space group Pm3̅m; x = 1.15, a = 4.0550(4) Å and x = 1.34, a = 4.0449(2) Å for YPtxB6-2x and YbPtxB6-2x, respectively; single-crystal X-ray diffraction]. Two possible variants of B/Pt ordering (space group P4/mmm) were created via a group-subgroup approach targeting the derived stoichiometry. The architecture of the type-I YPtxB6-2x structure model (a' = a, b' = b, c' = c) combines the 4.82 boron nets alternating with the layers of Y and Pt; the type-II YPtxB6-2x structure model (a' = 2a, b' = 2b, c' = c) exhibits columns of linked [B24] truncated cubes filled with Y running along the c axis. The striking features of both structural models are [B4Pt2] octahedra. The structural similarities with hitherto reported structures (YB2C2, M2Ni21B20, MNi21B20, and ErNiB4) were drawn supporting the verity of these models. A chemical bonding analysis for type-I and type-II YPtxB6-2x based on electron localization function distribution revealed a two-center interaction forming the 4.82 boron nets for type-I YPtxB6-2x and a covalent bonding within [B4Pt2] octahedra as well as a two-center interaction for B-B intraoctahedral bonds for type-II YPtxB6-2x. Analysis of Bader charges revealed the cationic character of the yttrium atoms. The interactions for nondistorted areas of the structures agree well with the bonding picture calculated for constituent building structures, YB6 and YPt3. Electronic structure calculations predict YPtxB6-2x to be a metal with the density of states of around N(EF) = 1 states eV-1 f.u.-1. The exploration of the Y-Pt-B system in the relevant concentration range elucidated the homogeneity field of YPtxB6-2x (0.90 ≤ x ≤ 1.40) and revealed the existence of three more ternary phases at 780 °C: YPt2B (space group P6222), YPt3B (space group P4mm), and YPt5B2 (space group C2/m).