The Rear Naked Choke
The rear naked choke is probably the most effective submission in MMA because once you take a person's back and apply a rear naked choke, it is essentially game over. The rear naked choke (RNC or mata leao) looks very simple to do. However, in reality, there is a lot of detail to make it work perfectly, especially in the set ups.
Here is an excellent clip on the little details to make your rear naked choke even more effective.
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