Reduced praseodymium cluster bromides stabilized by transition metals

Journal Article · Tue Mar 01 23:00:00 EST 1994 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00083a004· OSTI ID:7267569

Llusar, R; Corbett, J D ^[1]

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1. Iowa State Univ., Ames, IA (United States)

Reactions of Pr turnings, PrBr[sub 3], and metallic Z in Nb containers at 780-910[degrees]C yield Pr[sub 6]Br[sub 10]Z (Y[sub 6]I[sub 10]Ru type) for Z = Co, Ru, Os, monoclinic Pr[sub 3]Br[sub 3]Ru (Pr[sub 3]I[sub 3]Ru type), and cubic Pr[sub 3]Br[sub 3]Z (Ca[sub 3]PI[sub 3]type) for Z = Co, Os, Rh, Ir, Pt. Other Z elements investigated yield the binary Pr[sub 2]Br[sub 5] or unknown phases. The structures of Pr[sub 6]Br[sub 10]CO and Pr[sub 6]Br[sub 10]Ru have been refined (P[bar 1];Z = 1; a = 9.359(4), 9.206(4) [angstrom], b = 9.243(5), 9.505(3) [angstrom], c = 7.538(3), 7.606(4) [angstrom], [alpha] = 97.37(4), 97.08(4)[degrees], [beta] = 107.31(4), 107.47(4)[degrees], [gamma] = 110.17(3), 109.69(4)[degrees], R = 4.3, 5.2%, R[sub w] = 3.8, 6.7%, respectively). The tetragonal compression in the 16-electron Pr[sub 6]Br[sub 10]Ru (0.28 [angstrom] in d(Pr-Ru)) is notably greater than observed in the analogous Y[sub 6]I[sub 10]Ru, probably because of reduced matrix effects (repulsions) between the smaller bromide components. Earlier theoretical predictions regarding a one-over-two splitting of the parent t[sub lu[sup 4]] in the idealized octahedral iodide are therefore supported. The 17-electron Pr[sub 6]Br[sub 10]Co shows a possibly related compression of 0.12 [angstrom].

• OSTI ID: 7267569
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 33:5; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BROMIDES
BROMINE COMPOUNDS
COBALT BROMIDES
COBALT COMPOUNDS
COHERENT SCATTERING
CRYSTAL STRUCTURE
DIFFRACTION
HALIDES
HALOGEN COMPOUNDS
IRIDIUM COMPOUNDS
MOLECULAR STRUCTURE
OSMIUM COMPOUNDS
PLATINUM BROMIDES
PLATINUM COMPOUNDS
PRASEODYMIUM BROMIDES
PRASEODYMIUM COMPOUNDS
RARE EARTH COMPOUNDS
REFRACTORY METAL COMPOUNDS
RHODIUM BROMIDES
RHODIUM COMPOUNDS
RUTHENIUM BROMIDES
RUTHENIUM COMPOUNDS
SCATTERING
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION