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Many of the people on "To Catch a Predator" were charged with "Criminal solicitation of a minor" (or similar charges, as these are usually state charges and can vary from state to state).

Most of these charges contain a clause that reads - or is similarly worded to: "if he/she knowingly contacts or communicates with, or attempts to contact or communicate with, a person who is under the age of xx"

By this definition, it is not required that the person actually communicate with a minor, merely that they attempted to do so (usually by believing the person they're contacting is a minor and continuing to solicit them anyway).

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I think you're thinking of entrapment, when a police officer coerces someone into doing something illegal and then arrests them for it. Entrapment is a court defense, not a law in the usual sense of the word. Pedophiles caught in sting operations rarely get off on entrapment defenses, because the cops in this instance aren't coercing anyone into anything--they're laying bait online and letting people come to them.

And in the case of To Catch a Predator, it's even MORE irrelevant, since non-police citizens CAN'T do entrapment. It literally only applies if the person doing it is a cop, and those on the show weren't themselves police.