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SbF5 (antimony pentafluoride) is more stable than BiF5 (bismuth pentafluoride) primarily due to the differences in the central atoms' electronegativity and size. Antimony, being in the fifth group of the Periodic Table, has a suitable size and effective nuclear charge that allows for better bonding with fluorine atoms. In contrast, bismuth is larger and has a lower electronegativity, which leads to weaker Bi-F bonds and increased instability in BiF5. Additionally, the presence of lone pairs on bismuth contributes to steric and electronic repulsions, further destabilizing BiF5.

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