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The electronic and structural possibilities of a recently conceived, as-yet unsynthesized, AM6E8 (or A2M6E8) structural type are explored. With A an alkaline earth metal, M a transition metal, and E a main group element, a range of geometries containing M–M pairs with very short separations is feasible. Density functional theory geometry optimizations and an extended Hückel analysis of the bonding in a representative Ca2W6O8 realization support the qualitative picture of quadruple metal-metal bonding in these hypothetical phases. The MM pairs interact moderately (metallic behavior is anticipated) through linking atoms. Geometry optimizations of a wide range of hypothetical compounds show that the M–M separation in these will be in the range of realistic quadruple metal-metal bonding, 2.20–2.30 Å.
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Balakrishnarajan et al. (2004) studied this question.
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