A submission debut is when a submission is used for the first time ever in known MMA competition (though it might have been used in grappling and in minor competitions before, but we have almost no way of knowing that).
My list looks like this:
5. Kendall Grove's Brabo Choke victory over Alan Belcher.
I think the brabo choke is an underused sub in MMA, and I was happy that Kendall used it. Also, I love a good chokeout.
4. Dustin Hazelett's "overhook armbar" victory over Josh Byrkman.
IMO this submission was great because it seems like I can use it in practise in the future. In it's simplicity it's amazing that no one has thought of this submission before. What's even more awesome is that Hazelett basically made the move up right on the spot.
3. Nogueira's Anaconda Choke victory over Yokoi & Herring.
A debut choke is awesome, because chokes are awesome. That the commentators, including Bas and Chuck, don't know that it is a choke when they see it is awesome. Doing this submission BACK TO BACK is freakin' godly! Nuff said. (Plus, the technique is super - useful and really popular as a guillotine alternative if you have long arms)
2. Shinya Aoki's GoGo (Gadget)Platavictory over Joachim Hansen.
Hansen is awesome and a really solid fighter, but when Aoki comes in witht the rainbow pants, you can expect nothing but greatness. I don't even think I need to say why it's on the #2 spot on my list. JUST LOOK AT THAT SUB! Give's me a boner to see both the rubber guard utilized as it should be AND it leading to a finish.
1. Rumina Sato's flying armbar victory over some dude who is now Sato's living highlight reel. His name is Charles Taylor btw http://www.youtube.com/watch?v=xehQPfgJj7g I need to say no more...
The Medal of debut submissions goes to Imanari, because he has debuted with so many leglocks they deserve their own list. But I don't know when the first flying heel hook, for instance, was done, so I'll just give Imanari a super-honorary mention.