Catcher is a type of position where you can't skip steps. Most young catchers have to make their way through every level, before coming to the majors. You don't see many raw catchers in the MLB, especially during the regular season. If this was the case, Matt Wieters from the Orioles would be behind home plate for them right now.
Another thing to consider is the Yankees are paying Molina a lot. If he were on the Marlins, he would be their 3rd highest player. So he is going to be the primary catcher while Posada is gone. Therefore bringing Montero up to sit the bench or catch once or twice a week won't do him any good, it would stunt his growth.
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