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Crystals 2013, 3(3), 504-516;

Bonding Schemes for Polar Intermetallics through Molecular Orbital Models: Ca-Supported Pt–Pt Bonds in Ca10Pt7Si3

Department of Chemistry, University of Wisconsin—Madison, 1101 University Avenue, Madison, WI 53706, USA
Division of Polymers and Materials Chemistry, Lund University, P.O. Box 124, SE-221 00, Lund, Sweden
Author to whom correspondence should be addressed.
Received: 15 July 2013 / Revised: 16 August 2013 / Accepted: 20 August 2013 / Published: 3 September 2013
(This article belongs to the Special Issue New Trends in Intermetallics Development and Application)
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Exploratory synthesis in the area of polar intermetallics has yielded a rich variety of structures that offer clues into the transition in bonding between Zintl and Hume-Rothery phases. In this article, we present a bonding analysis of one such compound, Ca10Pt7Si3, whose large Ca content offers the potential for negative formal oxidation states on the Pt. The structure can be divided into a sublattice of Ca cations and a Pt–Si polyanionic network built from Pt7Si3 trefoil units linked through Pt–Pt contacts of 3.14 Å. DFT-calibrated Hückel models reveal that the compound adheres well to a Zintl-like electron counting scheme, in which the Pt–Si and Pt–Pt contacts are equated with two-center two-electron bonds. The experimental electron count is in excess of that predicted by 2%, a discrepancy which is attributed to the electron transfer from the Ca to the Pt–Si network being incomplete. For the Pt–Pt contacts, the occupancy of the bonding orbitals is dependent on the participation of the surrounding Ca atoms in bridging interactions. This use of multi-center interactions isolobal to classical two-center two-electron bonds may illustrate one path by which the bonds delocalize as one moves from the Zintl phases toward the Hume-Rothery domain. View Full-Text
Keywords: platinides; zintl phases; intermetallics; electronic structure platinides; zintl phases; intermetallics; electronic structure

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Fredrickson, D.C.; Doverbratt, I.; Ponou, S.; Lidin, S. Bonding Schemes for Polar Intermetallics through Molecular Orbital Models: Ca-Supported Pt–Pt Bonds in Ca10Pt7Si3. Crystals 2013, 3, 504-516.

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