K[sub 10]In[sub 10]Z (Z = Ni, Pd, or Pt): Zintl phases containing isolated decaindium clusters centered by transition elements
- Iowa State Univ., Ames, IA (United States)
The isostructural title compounds are obtained by high yield by slowly cooling the appropriate fused mixture in welded Ta. They occur in the orthorhombic space group Pnma, Z = 12, with a = 15.948(6), 16.043(6), 16.056(3) Angstroms, b = 32.565(6), 32.73(1) Angstroms, and c = 18.822(3), 18.895(5), 18.896(3) Angstroms for the Ni, Pd, and Pt derivatives, respectively. The structure of the Ni phase was refined by single crystal means (R, R[sub w] = 2.9, 3.3%) and shown to be constructed from the close-packed layers of Ni-centered In[sub 10] clusters that are separated by potassium ions both within and between the cluster layers. The compounds have large resistivities at room temperature by two-probe methods and are diamagnetic, with no moments on the transition metals. The geometry of the clusters can be derived from an ideal tetracapped trigonal prism (C[sub 3v]) of In centered by Z through axial compression along the 3-fold axis and opening of the capped triangular face so as to yield substantially equal Ni-In distances. The clusters are also related to Sb[sub 7][sup 3[minus]], etc. Charge-consistent extended Hueckel MO calculations show that the Ni-centered cluster has a closed shell with 2n = 20 skeletal electrons, only the s and p orbitals on the interstitial mixing with appropriate cluster orbitals. The d orbitals on Ni do not appear to participate significantly, presumably because they are fully reduced (lie too low) relative to In p (d(In-Ni) to approximately 2.8 Angstroms). Ths means that Ni, Pd, and Pt behave as quasi-main-group elements. 23 refs., 4 figs., 2 tabs.
- OSTI ID:
- 5065226
- Journal Information:
- Journal of the American Chemical Society; (United States), Vol. 115:20; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
INDIUM COMPOUNDS
CRYSTALLOGRAPHY
ELECTRONIC STRUCTURE
PHYSICAL PROPERTIES
NICKEL COMPOUNDS
PALLADIUM COMPOUNDS
PLATINUM COMPOUNDS
POTASSIUM COMPOUNDS
CATIONS
COMPILED DATA
SOLID CLUSTERS
TANTALUM COMPOUNDS
ALKALI METAL COMPOUNDS
CHARGED PARTICLES
DATA
INFORMATION
IONS
NUMERICAL DATA
REFRACTORY METAL COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
664100 - Theory of Electronic Structure of Atoms & Molecules- (1992-)