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Shiny Deoxys - Must state that it is from Birth Island from Fire Red/Leaf Green.Shiny Jirachi - Must state that it is from the Colosseum Bonus Disc or Pokémon Channel.
Shiny Events Allowed: Shiny Mew - Must state that it is from Faraway Island.
Shiny Darkrai - Must state that it is from the Member Card Event.
Ops are added when the other ops think that they should be added.
There is no way to "become an op" of your own doing, it is a granted access that you cannot ask for, and probably will not get if you make it apparent you're trying to get it.
Don't request/offer Pokémon that come from events that haven't happened yet. See the spoiler below for 6th-gen pokémon that are not allowed as of October, 2013.