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The experimental crystal structure of Tl2Pt(CN)4 suggests a molecular crystal. Theoretical calculations on the monomer give a much shorter Tl−Pt distance of 287.7 pm. The correlation-induced s2−d8 interaction strongly shortens the bond, but crystal-field effects are suggested to overcompensate for this contribution. The experimental UV bands are well-reproduced.
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Dolg et al. (1996) studied this question.
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