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So I was in a mystery dungeon when I came across a sleeping Klang. I got right up to it and tried using Thundershock on it. No damage done, Klang stayed asleep. Tried again with Quick Attack, no damage, still asleep. Not even my normal attacks or paralyzing it would wake it up.

So what's up with that then?

Location was the Mystery Dungeon you go to to rescue Dunsparce from the Pawnairds.

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In Pokemon Mystery Dungeon Gates to Infinity certain Pokemon may seem invincible to you but are not because those klang and other future Pokemon are higher level then you and the higher the level they are less likely you will hit and deal less damage. The only way to damage them that early is with set based damaging moves like dragon rage Axew or become higher level

Source played GtI many times

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Will these Pokemon always start out asleep?
If you are a lower level they will always be asleep until you somehow damage them, I don't remember if they wake up when your a higher level i haven't played in a while