Zintl cluster chemistry in the alkali-metal-gallium systems

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Previous research into the alkali-metal-gallium systems has revealed a large variety of networked gallium deltahedra. The clusters are analogues to borane clusters and follow the same electronic requirements of 2n+2 skeletal electrons for closo-deltahedra. This work has focused on compounds that do not follow the typical electron counting rules. The first isolated gallium cluster was found in Cs{sub 8}Ga{sub 11}. The geometry of the Ga{sub 11}{sup 7{minus}} unit is not deltahedral but can be described as a penta-capped trigonal prism. The reduction of the charge from a closo-Ga{sub 11}{sup 13{minus}} to Ga{sub 11}{sup 7{minus}} is believed to be the driving ... continued below

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37 p.

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Henning, R. March 27, 1998.

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This thesis or dissertation is part of the collection entitled: Office of Scientific & Technical Information Technical Reports and was provided by UNT Libraries Government Documents Department to Digital Library, a digital repository hosted by the UNT Libraries. It has been viewed 11 times . More information about this document can be viewed below.

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  • Ames Laboratory
    Publisher Info: Ames Lab., IA (United States)
    Place of Publication: Iowa

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Previous research into the alkali-metal-gallium systems has revealed a large variety of networked gallium deltahedra. The clusters are analogues to borane clusters and follow the same electronic requirements of 2n+2 skeletal electrons for closo-deltahedra. This work has focused on compounds that do not follow the typical electron counting rules. The first isolated gallium cluster was found in Cs{sub 8}Ga{sub 11}. The geometry of the Ga{sub 11}{sup 7{minus}} unit is not deltahedral but can be described as a penta-capped trigonal prism. The reduction of the charge from a closo-Ga{sub 11}{sup 13{minus}} to Ga{sub 11}{sup 7{minus}} is believed to be the driving force of the distortion. The compound is paramagnetic because of an extra electron but incorporation of a halide atom into the structure captures the unpaired electron and forms a diamagnetic compound. A second isolated cluster has been found in Na{sub 10}Ga{sub 10}Ni where the tetra-capped trigonal prismatic gallium is centered by nickel. Stabilization of the cluster occurs through Ni-Ga bonding. A simple two-dimensional network occurs in the binary K{sub 2}Ga{sub 3} Octahedra are connected through four waist atoms to form a layered structure with the potassium atoms sitting between the layers. Na{sub 30.5}Ga{sub 60{minus}x}Ag{sub x} is nonstoichiometric and needs only a small amount of silver to form (x {approximately} 2--6). The structure is composed of three different clusters which are interconnected to form a three-dimensional structure. The RbGa{sub 3{minus}x}Au{sub x} system is also nonstoichiometric with a three-dimensional structure composed of Ga{sub 8} dodecahedra and four-bonded gallium atoms. Unlike Na{sub 30.5}Ga{sub 60{minus}x}Ag{sub x}, the RbGa{sub 3} binary is also stable. The binary is formally a Zintl phase but the ternary is not. Some chemistry in the alkali-metal-indium system also has been explored. A new potassium-indium binary is discussed but the structure has not been completely characterized.

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37 p.

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OSTI as DE99002520

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  • Other Information: TH: Thesis (Ph.D.)

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  • Other: DE99002520
  • Report No.: IS-T--1840
  • Grant Number: W-7405-ENG-82
  • Office of Scientific & Technical Information Report Number: 350829
  • Archival Resource Key: ark:/67531/metadc684503

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  • March 27, 1998

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  • July 25, 2015, 2:20 a.m.

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  • Nov. 6, 2015, 9:05 p.m.

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Henning, R. Zintl cluster chemistry in the alkali-metal-gallium systems, thesis or dissertation, March 27, 1998; Iowa. (digital.library.unt.edu/ark:/67531/metadc684503/: accessed September 24, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.